氨基络合物制备氨硼烷及放氢性能研究

以NaBH₄为硼源、氨基络合物Ni(NH₃)₆Cl₂为氨源制备高储氢容量的氨硼烷(NH₃BH₃, Ammonia Borane, AB)及其放氢性能研究. 通过XRD, FTIR, ¹¹B NMR, ICP等手段分析表征了所制备产物的组成和纯度, 在此基础上探究了原料比例、反应温度、时间和溶剂等因素对产物的影响. 同时, 对不同原料比制得氨硼烷的热解放氢性能进行了研究. 实验结果表明: 当物质的量NaBH₄∶Ni(NH₃)₆Cl₂＝2∶1经过10 h的反应, 得到了纯度非常高的氨硼烷(纯度＞99%)|以NaBH₄∶Ni(NH₃)₆Cl₂＝3∶1得到的氨硼烷, 当以2 ℃/min进行升温时, 氢气释放主要集中在第一步, 并且没有硼烷和硼嗪等杂质气体的产生. 另外, 在产物中得到了金属Ni纳米颗粒, 经洗涤干燥后其粒径大小可控制在10 nm左右, 在催化氨硼烷等材料的水解放氢方面具有潜在的应用价值.     

取代基对胺硼烷热分解行为的影响

利用不锈钢高压反应釜内衬聚四氟乙烯反应器,对胺硼烷(RR′NHBH_3, R,R′=H, AB; R=H, R′=Me, MAB; R,R′=Me, DMAB)的热分解行为进行了研究.三种硼烷化合物的分解方式不同.氨硼烷(AB)在80～100℃下形成的聚合物产物[NH_2BH_2]_n,在高于110℃的温度下进一步转化为[NHBH]_3和[N_3B_3H_x]_n.甲基胺硼烷(MAB)则首先形成聚合产物[MeNHBH_2]_(3-)_x和[MeNHBH_2]_(2-)_x,然后进一步转化为[MeNBH]_3.二甲基胺硼烷(DMAB)的热分解过程中没有检测到聚合产物,相反,检测到[Me_2NBH_2]_2二聚体和(Me_2N)_2BH分子化合物生成,随后转化为(Me_2N)_3B.最后讨论了甲基取代对这些胺硼烷热分解行为的影响.     

碳硼烷硼端衍生物的合成与表征

在路易斯酸催化下,碳硼烷分别与对氰基溴化苄、三苯基膦在甲苯溶液里回流,前者反应中,制备得碳硼烷的硼端与对氰基苄基中的亚甲基直接偶联的产物1,通过调整催化剂的含量,可以显著地提高含B-Cl键的产物2的产率;与三苯基膦的反应中,碳硼烷失去一个硼顶,并与三苯基膦中的P原子直接偶联,生成含B-P键的巢式碳硼烷衍生物3。对此两类化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1和2中均发现碳硼烷的CH与N形成CH…N氢键和CH…π的弱作用,其中化合物2中,还存在CH…Cl。在巢式化合物3中,发现碳硼烷的CH参与了罕见的CH…HC相互作用。这类反应成功合成了含有B-C、B-Cl、B-P键的碳硼烷衍生物。     

碳硼烷结构规则的量子化学计算

本文对一系列封闭型C_nB_5-n(n=0～5)和C_nB_6-n(n=0～6)碳硼烷骨架及巢型C₄B_5-n(n=0～5)碳硼烷骨架进行了EHMO量子化学计算,根据计算结果讨论了碳硼烷的结构规则.     

多孔碳负载镍纳米颗粒的制备及催化氨硼烷水解制氢

合成了蜂窝状的分级多孔碳,并以多孔碳为载体通过浸渍-化学还原法制备碳载镍(Ni/C)作为催化氨硼烷水解制氢的催化剂。采用XRD、BET、SEM、Raman、TEM等手段对样品进行了表征并研究了Ni/C室温催化性能。结果显示,多孔碳比表面积高达737 m2·g-1,具有部分石墨化结构;负载的非晶态镍纳米颗粒平均粒径约为10 nm,均匀分布在碳基材。碳载镍对氨硼烷水解反应具有良好的催化活性,镍负载量为30wt%时催化性能最佳,298 K温度下放氢速率达到1 304.67 m L·min-1·g-1,活化能为29.1 k J·mol-1,并且具备一定的催化稳定性,表明Ni/C可作为一种廉价高效的催化剂应用于催化氨硼烷水解制氢。     

多孔碳负载镍纳米颗粒的制备及催化氨硼烷水解制氢

合成了蜂窝状的分级多孔碳,并以多孔碳为载体通过浸渍-化学还原法制备碳载镍(Ni/C)作为催化氨硼烷水解制氢的催化剂。采用XRD、BET、SEM、Raman、TEM等手段对样品进行了表征并研究了Ni/C室温催化性能。结果显示,多孔碳比表面积高达737 m²·g^-1,具有部分石墨化结构;负载的非晶态镍纳米颗粒平均粒径约为10 nm,均匀分布在碳基材。碳载镍对氨硼烷水解反应具有良好的催化活性,镍负载量为30wt%时催化性能最佳,298 K温度下放氢速率达到1 304.67 mL·min^-1·g^-1,活化能为29.1 kJ·mol^-1,并且具备一定的催化稳定性,表明Ni/C可作为一种廉价高效的催化剂应用于催化氨硼烷水解制氢。     

氨硼烷释氢纳米金属催化剂的研究

化学储氢材料要求具有高的氢存储容量。氨硼烷（NH₃BH₃,AB）的氢含量高达19.6 wt%,是一种具有潜在应用前景的氢存储介质。AB的水解释氢容量高达7.8 wt %,热解释氢则可释放出19.6 wt %的氢,显示出其在化学储氢方面的巨大潜力。在AB释氢研究中,催化剂是研究的核心技术和重要方向。由于纳米催化剂在AB释氢中所表现出的优良催化性能,本文将对氨硼烷释氢纳米金属催化剂及其性能的研究进行全面的总结和展望。     

碳硼烷和碳硼炔金属配合物中金属-碳键的化学性质

碳硼烷和碳硼炔金属配合物中的金属-碳键具有不同于经典金属-碳键的化学性质.一方面,二十面体碳硼烷独特的电子和空间效应使得碳硼烷金属配合物中的金属-碳键不参与和不饱和分子的反应 另一方面,在一定条件下具有大空间位阻的碳硼笼可以诱导某些碳-碳偶联反应.然而,碳硼炔金属配合物中的金属-碳键能与多种不饱和分子发生反应,其反应模式取决于中心金属离子的电子构型.本文简要总结了我们近期在这方面的研究进展.     

均相钴催化氨硼烷的脱氢及转移氢化反应的研究进展

作为理想的化学储氢材料,氨硼烷的高效脱氢和转移氢化的研究已经引起了越来越多的重视.由于丰产金属具有价廉易得和生物兼容性好等优势,丰产金属均相催化氨基硼烷的脱氢及相关转化,是该领域的重要发展方向.主要综述了代表性的均相丰产金属钴络合物催化的氨基硼烷的脱氢和转移氢化的研究进展.     

Ruthenium deposited on MCM-41 as efficient catalyst for hydrolytic dehydrogenation of ammonia borane and methylamine borane

Ultrafine Ru nanoparticles are successfully deposited on MCM-41 by using a simple liquid impregnationreduction method, and further investigated for catalytic hydrolysis of ammonia borane and methylamine borane. Among all the catalysts tested, 1.12 wt% Ru/MCM-41 exhibits the highest catalytic activity, with turnover frequency value of 288 min^-1.     

Thermal conductivity of ammonia borane complex and its composites with aluminum powder

The thermal conductivity of ammonia borane (AB) complex, in the temperature range of 300-420 K, was measured experimentally using ASTM method E 1225. At 300 K, the thermal conductivity of pure AB was found to be approximately 15 W/m-K. A composite pellet prepared by mixing 10 wt% aluminum powder with AB had a thermal conductivity that was a factor of 4 higher than that of pure AB complex. The extent of the pyrolytic weight loss for AB/Al composite and pure AB complex was 25.4% and 33.9%, respectively—indicating comparatively lower levels of volatile species evolved as impurities (e.g. monomeric aminoborane, borazine, diborane, etc.) in the product hydrogen.     

Catalytic dehydrogenation of natural terpenes via CuPd alloy nanoparticles generated on mesoporous graphitic carbon nitride

A facile wet-chemical protocol for the synthesis of bimetallic CuPd alloy nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (m-gCN), serving as both stabilizer and support material, was presented herein. The presented protocol allowed to synthesize nearly monodisperse CuPd alloy NPs with an average particle size of 3.9 ± 0.9 nm without use of any additional surfactants and to prepare CuPd/m-gCN nanocatalysts with different Cu/Pd compositions (Cu₂₅Pd₇₅/m-gCN, Cu₃₅Pd₆₅/m-gCN, Cu₁₆Pd₇₄/m-gCN, Cu₃₂Pd₆₈/m-gCN, Cu₁₀Pd₉₀/m-gCN, and Cu₅₀Pd₅₀/m-gCN). After the detailed characterization of CuPd/m-gCN nanocatalysts, they were utilized as catalysts in the dehydrogenation of terpenes. Among all tested nanocatalysts, Cu₅₀Pd₅₀/m-gCN showed the highest activity in terms of the product yields within the same reaction time. Various parameters influencing the catalytic activity of Cu₅₀Pd₅₀/m-gCN were studied using himachalene as a model substrate and the optimum conditions were determined. Under the optimized reaction conditions, the catalytic application of Cu₅₀Pd₅₀/m-gCN nanocatalysts was extended to nine different terpenes and the corresponding products were obtained in high conversion yields (>90%) under mild conditions. A reusability test showed that Cu₅₀Pd₅₀/m-gCN nanocatalysts can be re-used up to four cycles without significant loss in their initial activity.     

石墨相氮化碳负载钒作为多相催化剂用于苯直接氧化制苯酚

苯酚是一种重要的化工原料,目前苯酚的工业生产路线普遍存在工艺流程复杂、苯酚收率低和环境污染严重等问题.为实现苯酚的绿色生产,苯直接氧化制苯酚的合成路线受到各国研究者的广泛关注.在苯直接羟基化反应常用的 N2O, O2和 H2O2三类氧化剂中, N2O由于来源有限,其工业应用受到极大限制;而 O2不易活化,且反应过程中常需还原剂存在,苯酚收率低;相比之下, H2O2作为氧化剂,其唯一副产物是 H2O,而且反应条件温和,因而以 H2O2为氧化剂的苯羟基化反应是最具工业应用前景的苯酚合成路线.然而,由于苯分子中的 C?H键非常稳定,活化能较高,同时产物苯酚的反应活性要高于反应物苯,因此,为实现苯的高效转化,积极探索研究高活性和稳定性的催化剂变得尤为重要.在我们之前的研究中发现,包含大π体系的氧化石墨烯载体有利于具有同样π共轭体系的反应物苯的吸附,进而促进苯的转化,提高反应活性.而石墨相氮化碳(g-C3N4)具有与氧化石墨烯类似的π共轭体系,且表面具有大量的活性位点和缺陷位,对苯环类物质具有较好的活化作用,这使其可能成为更优异的载体材料.基于此,以 g-C3N4为载体,采用浸渍法制备了一系列不同钒含量的催化剂xV/g-C3N4,并通过 XRD, FT-IR, TEM, TG等表征技术对催化剂进行了系统研究,以期揭示催化剂结构与反应活性之间的构效关系. XRD的表征结果表明,xV/g-C3N4仍具有载体 g-C3N4的层状堆积结构,且该结构不受钒负载量变化的影响.同时, xV/g-C3N4中钒物种的分散度较高,未发生团聚晶化.更直观地,通过 TEM观察发现,xV/g-C3N4中的钒物种均匀分散. FT-IR的表征结果说明钒物种与 g-C3N4之间存在较强的相互作用.此外,通过 TG表征发现, g-C3N4高温稳定性较好,即使焙烧温度高达550°C,其结构仍不受影响.综上所述,在xV/g-C3N4催化剂中,载体 g-C3N4的结构非常稳定,经负载钒物种以及焙烧处理后仍能保持不变;而钒物种与 g-C3N4之间存在较强的相互作用,且均匀分散,使催化剂具有较高的稳定性和较好的催化性能.在以 H2O2为氧化剂,80 wt%醋酸溶液为溶剂的苯直接氧化制苯酚反应中,xV/g-C3N4催化剂显示了良好的催化活性,其中反应活性最高的是8V/g-C3N4催化剂,在最佳反应条件下,苯酚的收率和选择性分别达到24.4%和99.2%.同时,通过计算 TOF值发现,8V/g-C3N4的 TOF值高达13.1 h-1,远高于文献中报道的以 C3N4为载体的催化剂的 TOF值(0.52–0.59 h-1),这表明xV/g-C3N4催化剂具有优异的催化活性.此外,以8V/g-C3N4为代表又进一步考察了催化剂的稳定性,在回收重复实验中催化剂的活性保持稳定.     

Effect of thickness on the photophysics and charge carrier kinetics of graphitic carbon nitride nanoflakes

The thickness of graphitic carbon nitride nanoflake has an obvious effect on its bandgap and charge carrier kinetics.     

Hydrogen generation of ammonia borane hydrolysis catalyzed by Fe22@Co58 core-shell structure

In this paper, the process of ammonia borane (AB) hydrolysis generate H₂ on the transition metal Fe@Co core-shell structure has been obtained. According to the different roles played by H₂O molecules and the number of H₂O molecules involved, there are three schemes of reaction paths. Route I does not involve the dissociation of H₂O molecules and all H atoms come from AB. Moreover, the H₂O molecule has no effect on the breaking of the BH bond or the NH bond. The reaction absorbs more heat during the formation of the second and third H₂ molecules. Route II includes the dissociation of H₂O molecules and the cleavage of BH or NH bonds, respectively, and the reaction shows a slight exotherm. Route III started from the break of the BN bond and obtained 3H₂ molecules through the participation of different numbers of H₂O molecules. After multiple comparative analyses, the optimal hydrolysis reaction path has been obtained, and the reaction process can proceed spontaneously at room temperature.     

Spectroscopic studies of dehydrogenation of ammonia borane in carbon cryogel

Ammonia borane (AB) is of great interest for storing hydrogen, an important issue in the growing field of hydrogen technology. The reaction pathways leading to the thermal decomposition of solid-state AB incorporated in carbon cryogels (CC) have been studied by spectroscopic methods. The time-dependent thermal decomposition was followed by in situ 11B nuclear magnetic resonance (NMR) and showed a significant increase in hydrogen release kinetics for AB in CC compared to neat AB. Both 11B NMR and Fourier transform infrared spectroscopy show a new reaction product, formed in the thermal decomposition of AB in CC scaffold (CC-AB) that is assigned to reactions with surface oxygen groups. The results indicate that incorporation of AB in CC enhances kinetics because of the reactions with residual surface-bound oxygen functional groups. The formation of new products with surface -O-B bonds is consistent with the greater reaction exothermicity observed when hydrogen is released from CC-AB materials. Scanning electron microscopy shows different morphology of AB in CC-AB nanocomposite as compared to neat AB.     

Regulating ambient pressure approach to graphitic carbon nitride towards dispersive layers and rich pyridinic nitrogen

An ambient pressure-induced calcination process was proposed to prepare g-C_3 N_4 with different structures.The porcelain boat with designed porosity is used to control the ambient pressure to change the diffusion behavior of the reaction molecules,thereby controlling the layer structure and rich pyridinic N content of g-C_3 N_4,thus renders superior lithium storage performance.     

Bifunctional copper modified graphitic carbon nitride catalysts for efficient tetracycline removal: Synergy of adsorption and photocatalytic degradation

In order to efficiently remove tetracycline in wastewater through the synergistic effect of adsorption and photocatalytic degradation, a series of novel composite materials (Cu doped g-C₃N₄) were synthesized by two-pot hydrothermal method. It was found that the composite materials with optimized ratio (Cu/CN-1) displayed outstanding adsorption and photocatalytic performance as compared with pure g-C₃N₄ photocatalyst. The removal efficiency of tetracycline (TC, 50 mg/L) reached almost 99% within 30 min by Cu/CN-1 through the synergy of adsorption and photocatalysis under visible-light irradiation, which was the highest removal efficiency ever reported. The adsorption kinetics and isotherms of TC on the Cu/CN-1 were well fitted with the pseudo-second-order kinetic model and Langmuir model, respectively. Moreover, it was confirmed that the main effective reactive groups were O₂⁻ and h⁺ in photocatalytic process. The Cu/CN-1 exhibited high stability and excellent reusability after five cycle experiments. Finally, the mechanism of synergy between Cu and g-C₃N₄ was proposed: on the one hand, the decoration of Cu particles significantly increased the adsorption sites of Cu/CN-1 to tetracycline, on the other hand, the modification of Cu particles effectively inhibits charge recombination and broadens the visible light absorption range of the photocatalyst.This study provided a promising photocatalyst to be used for TC removal in the actual wastewater.