氮化硼纳米管-纳米片分级结构的制备及光学和吸附特性

将五硼酸铵、 氨硼烷络合物和氧化镁混合, 球磨均匀后, 在1200 ℃及0.6 L/min流动氨气保护条件下退火6 h, 即可在氧化铝基片上收集到白色毛状产物. 采用X射线衍射(XRD), 红外光谱(FTIR)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 拉曼光谱(Raman)、 紫外-可见吸收光谱(UV-Vis)和荧光光谱(PL)对产物进行了表征. 结果表明, 样品呈一维线状分级结构, 长度大于5 mm, 中间为竹节状空心结构, 内部管径为50~350 nm, 外径范围为200~800 nm. 分级结构表面负载了大量氮化硼(BN)纳米薄片, 单个薄片厚度约为13 nm. 薄片弯曲褶皱, 相互交织, 构成1个氮化硼片层, 其厚度约为50~200 nm. UV-Vis和PL光谱测试结果表明, 氮化硼纳米管(BNNT)分级结构在紫外光材料领域具有一定的应用潜力, 且对亚甲基蓝具有良好的吸附能力(7 min即可吸附71%, 107 min时可吸附96%). 对比实验结果表明, BNNT的生长机理遵循气-液-固相(VLS)模型, 而表面负载的超薄BN片的生长机理遵循气-固相(VS)模型.     

氮化硼/聚合物导热复合材料研究进展

电子信息产业的高速发展,使得电子装置或装备在使用过程中产生的热量越来越剧烈,需要及时导出以保证其正常运行,聚合物基导热复合材料由于其优异的加工性和较低的成本得到了应用。六方氮化硼(h-BN)兼具优异的导热性和绝缘性,因此作为导热填料在导热绝缘聚合物复合材料领域受到越来越多的关注。本文主要从氮化硼填料尺寸、表面性质、取向结构以及杂化等方面综述了近年来氮化硼/聚合物导热复合材料的研究进展。     

Theoretical studies of third-order nonlinear optical response for B12N12, B24N24 and B36N36 clusters

In this paper, we have calculated the third-order nonlinear optical polarizabilities corresponding to three optical processes: third-harmonic generation (THG), electric-field-induced second-harmonic generation (EFISHG) and degenerate four-wave mixing (DFWM) for B₁₂N₁₂, B₂₄N₂₄ and B₃₆N₃₆ clusters. The calculations have been performed by employing ab initio time-dependent density functional theory combined with sum-over-states method (SOS//TDDFT). We obtained the similar dynamic behavior of third-order NLO polarizabilities for three BN clusters. At input photon energy below 1.25 eV, the resonance enhancements of response haven't occurred. This is due to the fact that the calculated BN clusters have the large transition energy. B₂₄N₂₄ cluster has the larger transition dipole moments and the third-order polarizabilities of B₂₄N₂₄ are much larger than those of B₁₂N₁₂ and B₃₆N₃₆. We also estimate the static third-order optical susceptibility χ⁽³⁾ for BN fullerene materials from the average static third-order polarizability <γ>. The static χ⁽³⁾ of B₂₄N₂₄ fullerene materials are 1.36×10⁻¹⁴ esu for three NLO processes.     

(Me3Si)2NBCl2和(Me3Si)2NB(Cl)NHSiMe3的合成及其成环反应

自从氮化硼陶瓷纤维用聚合物先驱体法[1]合成以后,硼氮六元环化合物越来越为人们所重视[2],文中在制备氮化硼纤维先驱体的过程中,合成了其中间产物,通过热缩合成环反应,合成了含有硼氮六员环的化合物,并采用色-质联用技术对其进行了表征。1　实验部分参照文献[3],改用液氮和丙酮为冷冻剂,控制温度在-50到-40℃,搅拌下向三氯化硼的正戊烷溶液中缓慢滴加三乙胺的正戊烷溶液,滴完后Ｎ2气氛下-50℃加丙酮冷凝回流2ｈ,慢慢由-50℃升至室温,抽滤即得到白色产物Ｅｔ3ＮＢＣｌ3(Ａ)。将Ａ溶于适量苯中[4,5],加入等物质的量的三乙胺,加热回流搅拌…     

Simple synthesis of mesoporous boron nitride with strong cathodoluminescence emission

Mesoporous BN was prepared at 550 °C for 10 h or so via a simple reaction between NaBH₄ and CO(NH₂)₂. X-ray diffraction demonstrates the formation of t-BN with lattice constants a=2.46 and c=6.67 Å. High-resolution transmission electron microscopy displays a lot of porous films in the product, which possesses a high surface area of 219 m² g⁻¹ and a pore size primarily around 3.8 nm tested by nitrogen adsorption-desorption method. The mesoporous BN exhibits a strong luminescence emission around 3.41 eV in the cathodoluminescence spectra, a high stability in both morphology and structure, and good oxidation resistance up to 800 °C. The byproducts generated during the reaction are responsible for the formation of the mesoporous BN.     

Co掺杂的YBa2Cu2O6+δ的氧非计量和氧渗透性能研究

研究钴离子部分取代铜离子对YBa2Cu3O6+δ的氧非计量值δ和氧渗透率的影响.对于钴替代的样品,氧非计量的绝对值变大,且其数值不再随温度和氧分压的变化发生显著变化.YBa2Cu2CoO6+δ样品在中、高温具有可观的氧渗透率.对于厚度为1.2 mm的致密YBa2Cu2CoO6+δ样品,在850℃时,只要在样品两端施加较小的氧分压差(PO2=21.2 kPa、 PO2=101 Pa),其氧渗透率即可达57 μmol/cm2 s, 明显高于YBa2Cu3O6+δ的氧渗透率(31 μmol/cm2 s).YBa2Cu2CoO6+δ的高氧渗透率在结构上可被归结为位于晶胞基面上的氧离子和氧空位的均匀分布.     

(BN)n富勒烯和单层BN纳米管的图形理论方法研究

应用图形理论方法对(BN)12等富勒烯和单层BN纳米管的能级分布及其稳定性进行研究,发现(BN)n比同构型的(C2)n稳定,且与用DFT方法计算的结果一致.计算结果表明,采用图形理论方法是一种很有意义的解释和预测BN纳米材料的结构和性质的定性研究方法.     

B28N28笼的稳定性及笼中四元环间键联类型对笼稳定性的影响

采用密度泛函方法对四、六元环组成的所有可能的的23个笼状B28N28结构进行了理论计算和拓扑学特性研究, 用三个指标N4x4(x=0, 1, 2)来描述相邻四元环间的键联类型, 结果发现B28N28笼的相对能量随N4x4值的增大而增大, 且N404对稳定性的影响起主导作用. 这一简单的拓扑学标准可以给出所有四六结构B28N28异构体的大致能量顺序, 并从ISR结构中挑选出能量较低的结构, 因此有望用于挑选大尺寸氮化硼团簇的热力学稳定结构.     

Multi-walled BN nanotubes synthesized by carbon-free method

Pure multi-walled BN nanotubes were synthesized via a carbon-free chemical vapor deposition process using boron and gallium oxide mixture as reaction precursor. Transmission electron microscopy was used to investigate their structure, morphology and defects. The wall deformation, dependent on tube diameter, was observed and explained in terms of strain relaxation of bond rotation. Opposed to carbon nanotubes, bending of BN nanotubes typically results in fracture at their concave side. Ring defect-related mechanism was proposed to interpret the fracture. The ring defects also result in the formation of a nanocone with 300° disclination. The nanocones end up with BN nanotubes exhibiting the small innermost shell ∼0.4 nm in diameter.     

Effect of dopant valence on the oxygen desorption and oxygen permeability of SrCo0.4Fe0.5M0.1O3-δ》(M=Ni, A1 and Zr) mixed-conducting oxides

The effect of dopant valence on oxygen desorption and oxygen permeability of SrCo0.4Fe<0.5>M0.1O3-δ(M=Ni, Al and Zr) mixed-conducting oxides were investigated in detail by O2-TPD and oxygen permeation measurement. The SrCo0.4Fe0.5M0.1O3-δ for M=Fe, Ni, AI and Zr were denoted as SCF, SCFN, SCFA and SCFZ, respectively. O2-TPD analysis revealed that the amount of α oxygen desorption decreased with increasing the valance of doped metal elements (SCFN>SCFA≈SCF>SCFZ). The oxygen permeation flux at the temperature higher than 1148 K decreased in the order of SCFN>SCF>SCFZ>SCFA. Single activation for oxygen permeation was observed for SCFZ oxide and the activation energies of SCF and SCFA change at around 1073K, while the change temperature of SCFN was about 1173K.     

Effect of dopant valence on the oxygen desorption and oxygen permeability of SrCo0.4Fe0.5M0.1O3-δ （M -Ni,Al and Zr） mixed-conducting oxides

The effect of dopant valence on oxygen desorption and oxygen permeability of SrCo0.4Fe0.5M0.1O3-δ （M = Ni, Al and Zr） mixed-conducting oxides were investigated in detail by O2-TPD and oxygen permeation measurement. The SrCo0.4Fe0.5M0.1O3-δ for M = Fe, Ni, Al and Zr were denoted as SCF, SCFN, SCFA and SCFZ, respectively. O2-TPD analysis revealed that the amount of α oxygen desorption decreased with increasing the valance of doped metal elements （SCFN 〉 SCFA SCF 〉 SCFZ）. The oxygen permeation flux at the temperature ≈igher than 1148 K decreased in the order of SCFN 〉 SCF 〉 SCFZ 〉 SCFA. Single activation for oxygen permeation was observed for SCFZ oxide and the activation energies of SCF and SCFA change at around 1073 K, while the change temoerature of SCFN was about 1173 K.     

Synthesis of ultraviolet luminescent turbostratic boron nitride powders via a novel low-temperature, low-cost, and high-yield chemical route

A novel chemical route has been established for the synthesis of ultraviolet luminescent turbostratic boron nitride (t-BN) powders, by the reaction of NH₄BF₄ with NaNH₂ at 320 °C for 10 h, and the yield is as high as 90%. The synthesized brown-yellow samples were characterized by XRD, XPS, FT-IR, SAED, and HRTEM, which matched with t-BN. The electronic and optical properties of the product were investigated by PL and UV absorption. UV spectra revealed that the product has two obvious band gaps (∼5.8 and 4.6 eV) and PL spectra showed that it has an ultraviolet emission at 337 nm (). SEM image indicated that the particle size of the synthesized t-BN is mainly in the range of 1-10 μm. The renascent BF₃ and Na₃N intermediates are believed to be responsible for the growth of t-BN under mild conditions.     

Borylborazines as new precursors for boron nitride fibres

A variety of borylborazine-based polymers were successfully converted into boron nitride fibres via the preceramic polymer route. In this procedure, four monomers were polycondensed into highly tractable polymers which could be easily melt-spun into fine-diameter green fibres. These polymeric filaments were then transformed into boron nitride fibres after a well-defined heat-treatment at 1800 °C in a controlled atmosphere. All the resulting ceramic fibres were mechanically tested. In particular, results showed that the promising mechanical properties for two of the polymer-derived fibres were closely related to the structural units of the corresponding preceramic polymers.     

羟基化氮化硼催化乙烷氧化脱氢制乙烯

乙烯是最为重要的化工原料之一,目前其工业来源主要来自于烃类的水蒸汽裂解过程.该过程本质上是一个高温均相裂解过程,温度(>800?℃)高,能耗大,碳排放严重.乙烷氧化脱氢制乙烯属于放热反应,反应温度低,速率快,无积碳等限制,是一条更富有竞争力的工艺路线.然而,常用的金属或金属氧化物催化剂容易导致乙烯深度氧化,从而降低了乙烯选择性.纳米碳材料在烃类氧化脱氢反应中展现出一定的催化活性,但容易被氧化,难以用于反应温度高的乙烷氧化脱氢反应.本文报道了羟基化的氮化硼(BNOH)可高效催化乙烷氧化脱氢制乙烯.氮化硼边沿羟基官能团脱氢生成了动态活性位,从而引发了乙烷的脱氢反应.BNOH对乙烷氧化脱氢制乙烯显示出高选择性.当乙烷转化率在11%,乙烯选择性可高达95%;当乙烷转化率增加到40%,乙烯选择性保持在90%.重要的是,当乙烷转化率超过60%时,BNOH仍然可保持80%的乙烯选择性以及50%的乙烯收率.这些性能指标与现有工业乙烷水蒸气裂解过程运行性能相当.进一步优化反应条件,BNOH催化剂能够实现高达9.1 gC2H4 gcat-1 h-1的时空收率.经过200 h的氧化脱氢反应测试,BNOH催化剂活性和选择性基本恒定,表明其具有非常好的稳定性.X射线粉末衍射结果显示,反应前后BNOH催化剂的物相没有发生变化.透射电子显微镜测试证实,反应后BNOH催化剂的形貌和微观结构也没有明显改变.X射线光电子能谱结果显示,反应200 h后BNOH催化剂表面的氧含量仅从反应前的6.9 atom%微增到8.3 atom%.1H固体核磁共振谱测试显示,反应200 h后,BNOH催化剂上羟基含量无明显改变.结合原位透射红外光谱和同位素示踪实验,初步确定了BNOH催化剂上引发乙烷氧化脱氢反应的活性中心.氮化硼边沿的氧官能团并不能引发乙烷的氧化脱氢反应,而羟基官能团才是氧化脱氢反应发生的活性位.在乙烷氧化脱氢条件下,分子氧脱除羟基官能团上的氢原子动态生成BNO·?和HO2·?活性位.密度泛函理论计算表明,乙烷首先在BNO·?或HO2·?位活化生成乙基自由基,这些中间物进一步与气相氧物种发生反应脱氢生成乙烯.动力学测试结果也验证了上述实验和理论结果.     

高密度聚乙烯复合导热材料性能

将氮化硼(BN)与高密度聚乙烯(HDPE)熔融共混制备具较高导热性的HDPE/BN复合材料。 通过断面形态观察、热学性能、流变性能、力学性能和导热性能研究,讨论了BN质量分数对复合材料性能的影响。 结果表明,随着BN质量分数增加,BN颗粒逐渐聚集形成导热通道。 当BN质量分数为30%时,复合材料的导热系数达到1.00 W/(m·K),与纯HDPE相比提高156%。 同时复合材料的弹性模量提高75%,冷结晶温度提高1.5 ℃,熔体黏度和模量提高2倍。 证明BN不仅改善了复合材料的流变性和冷结晶,还提高了复合材料的导热性和弹性模量。     

B<Subscript>24</Subscript>N<Subscript>24</Subscript> nanocages: a GIAO density functional theory study of <Superscript>14</Superscript>N and <Superscript>11</Superscript>B nuclear magnetic shielding and electric field gradient tensors

Abstract  Density functional theory (DFT) calculations were performed to determine boron-11 and nitrogen-14 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) spectroscopy parameters in the three most stable B₂₄N₂₄ fullerenes for the first time. The considered samples were first allowed to relax entirely, and then the NMR and NQR calculations were performed on the geometrically optimized models. The calculations of the ¹¹B and ¹⁴N nuclear magnetic shielding tensors and electric field gradient tensors employed the Gaussian 98 software implementation of the gauge-including atomic orbital (GIAO) method using the Becke3, Lee-Yang-Parr (B3LYP) DFT level and 6-311G** and 6-311++G** standard basis sets in each of the three optimized forms, and converted the results to experimentally measurable NMR parameters.The calculated NMR chemical shieldings of the three cages show significant differences, providing a way to identify these clusters. The evaluated NQR parameters of the ¹¹B and ¹⁴N nuclei in the clusters are also reported and discussed. Graphical abstract