A high-resolution MAS NMR study on the potential catalysts Mo/HBeta for olefin metathesis: The interaction of Mo species with HBeta zeolite

The interfacial interaction of Mo species with the HBeta zeolite was studied by multinuclear MAS NMR, XRD and N₂ adsorption. As proved by the quantitative ²⁷Al MAS NMR, this interaction is so strong as to dealuminate the framework of HBeta, and leads to a new peak appearing at −14 ppm, which indicates the formation of crystalline Al₂(MoO₄)₃. This can also be detected by XRD measurements when the Mo loading is as high as 9.0 wt.%. The corresponding quantitative ²⁹Si and ¹H MAS NMR spectra show that the amount of silanols and Brønsted acidic sites decrease obviously with increasing Mo loading. This also reveals an interaction between Mo species and HBeta support through an oxygen bridge resulting from condensation with the hydroxyls on the support. At higher Mo loadings, the interaction is so strong that it results in an extraction of aluminum from the zeolite framework, and subsequently appearance of Al₂(MoO₄)₃ and loss of Brønsted acidic sites. These can be correlated to the low catalytic activity of Mo/HBeta in metathesis of ethylene and 2-butylene to propylene.     

Pb intercalation underneath a graphene layer on Ru(0001) and its effect on graphene oxidation

Intercalation of Pb at graphene/Ru(0001) interfaces has been dynamically observed using in situ low energy electron microscopy and photoemission electron microscopy. A comparative study of Pb intercalation on the submonolayer and complete monolayer graphene surfaces suggest that the Pb intercalation happens through the open edges of graphene islands, starting at around 150 °C. Spatially-resolved low energy electron diffraction measurements reveal that the Pb-intercalated graphene overlayers are quasi-free-standing. The intercalated graphene sheets show lower reactivity to oxidation in O(2).     

High-rate cathode based on Li3V2(PO4)3/C composite material prepared via a glycine-assisted sol–gel method

Carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP/C) cathode material has been successfully prepared by a novel glycine-assisted sol–gel method. The product is investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM) and electrochemical method. In the range of 3.0–4.3 V, the LVP/C electrode presents excellent rate capability. It is 125.4 mAh g^{− 1} that can be delivered at 1 C charge–discharge rate and 99.5 mAh g^{− 1} is still obtained at 20 C charge–discharge rate. These results demonstrate that the carbon-coated LVP/C composite material prepared via a glycine-assisted sol–gel method has great potential for use in high-power lithium ion batteries.     

Interactions of phosphorous molecules with the acid sites of H-Beta zeolite: Insights from solid-state NMR techniques and theoretical calculations

The local structures of various Brønsted and Lewis acid sites in H-Beta zeolite were resolved with the combined ³¹P MAS NMR, ³¹P–²⁷Al TRAPDOR NMR experiments and theoretical calculations at different levels. In addition, the interacting mechanisms of these acid sites with probe molecules such as trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO) were clarified, which greatly aids the understanding of acid catalysis. Owing to the narrow chemical shift range and close Brønsted acid strengths, only an average resonance at −4.5 ppm was observed in TMP adsorbed H-Beta zeolite, consistent with the calculated data of acidities (substitution energies and proton affinities), geometries, adsorption energies as well as ³¹P chemical shifts. However, two types of Brønsted acids were distinguished by TMPO, and the HF/DZVP2 (MP2/DZVP2) chemical shifts were calculated at 68.1 (69.5) and 69.7–72.1 (71.7–74.9) ppm, respectively. Two types of Lewis acids were identified at −32.0 and −47.0 ppm with the latter exhibiting strong ³¹P–²⁷Al TRAPDOR effects. With theoretical calculations, these two peaks were attributed to the extra-lattice oxo-AlOH²⁺ species and the three-fold coordinated lattice-Al, extra-framework Al(OH)₃, oxo-AlO⁺ species, respectively. The peak at −60.0 ppm was conventionally assigned to the TMP physisorption, but the calculations indicated that the EFAL monovalent Al(OH)₂⁺ species coordinating with two lattice-O atoms near the framework Al atom can contribute to it as well.     

C−C Bond Formation in Syngas Conversion over Zinc Sites Grafted on ZSM‐5 Zeolite

Despite significant progress achieved in Fischer–Tropsch synthesis (FTS) technology, control of product selectivity remains a challenge in syngas conversion. Herein, we demonstrate that Zn²⁺‐ion exchanged ZSM‐5 zeolite steers syngas conversion selectively to ethane with its selectivity reaching as high as 86 % among hydrocarbons (excluding CO₂) at 20 % CO conversion. NMR spectroscopy, X‐ray absorption spectroscopy, and X‐ray fluorescence indicate that this is likely attributed to the highly dispersed Zn sites grafted on ZSM‐5. Quasi‐in‐situ solid‐state NMR, obtained by quenching the reaction in liquid N₂, detects C₂ species such as acetyl (‐COCH₃) bonding with an oxygen, ethyl (‐CH₂CH₃) bonding with a Zn site, and epoxyethane molecules adsorbing on a Zn site and a Brønsted acid site of the catalyst, respectively. These species could provide insight into C?C bond formation during ethane formation. Interestingly, this selective reaction pathway toward ethane appears to be general because a series of other Zn²⁺‐ion exchanged aluminosilicate zeolites with different topologies (for example, SSZ‐13, MCM‐22, and ZSM‐12) all give ethane predominantly. By contrast, a physical mixture of ZnO‐ZSM‐5 favors formation of hydrocarbons beyond C₃₊. These results provide an important guide for tuning the product selectivity in syngas conversion.     

Size-dependent surface reactions of Ag nanoparticles supported on highly oriented pyrolytic graphite

Various sizes of Ag particles were grown on highly oriented pyrolytic graphite (HOPG) surfaces, which had previously been modified with nanopits to act as anchoring sites. Surface reactions of O2, CHCl3, and CCl4 on the Ag particles and bulk Ag(111) surfaces were studied by X-ray photoelectron spectroscopy (XPS), and it has been shown that size dependence of O2 and CHCl3 reactions on Ag differs from that of CCl4. Weak reactions of O2 and CHCl3 were observed on the bulk Ag(111) surfaces, while strong reactions occur on Ag particles with medium Ag coverage, suggesting that the reactions are controlled by the number of surface defect sites. On the contrary, the dissociation of CCl4 is mainly determined by the exposed Ag facet area, mainly Ag(111) facet, and strong dissociation reaction happens on the bulk Ag(111) surface. The results suggest that the size effects, which are often discussed in heterogeneous catalysis, are strongly dependent on the reaction mechanism.     

希土取代苯基化合物的合成

1970年Hart等利用苯基锂的乙醚溶液与希土氯化物的四氢呋喃悬浮液反应,首次合成了希土苯基化合物(C_6H_5)_3Ln(Ln=Sc、Y),LiLn(C_6H_5)_4(Ln=La、Pr),但没有得到满意的碳氢分析数据,碳的实测值仅为计算值的三分之二左右。其他希土苯基化合物的合成也有报道。为了进一步探索希土芳基化合物的合成方法,希土和芳基之间成键的可能性,我们使用邻甲氧基苯基锂和对甲基苯基锂与希土氯化物反应,试图合成新的希土取代苯基化合物。     

甲烷在Mo/HZRP-1催化剂上无氧脱氢芳构化反应Ⅰ.Mo/HZRP-1催化剂的催化性能和积炭行为

用高 硅含磷五 员环 沸 石 分子 筛（ 商 品 代号 Ｈ Ｚ Ｒ Ｐ１） 作 为 载体 ，制 备 了 Ｍｏ／ Ｈ Ｚ Ｒ Ｐ１ 催化剂． 与 Ｍｏ／ Ｈ Ｚ Ｓ Ｍ５ 相比， Ｍｏ／ Ｈ Ｚ Ｒ Ｐ１ 对 甲烷无 氧脱氢芳 构化反 应也表现 出较好的 催化 性能 ． 实验过程 中，在反 应气中添 加 Ｎ２ 作 为内标 物，给出包 括甲烷 在 Ｍｏ／ Ｈ Ｚ Ｒ Ｐ１ 上 的结焦量 、转化率 及各产物选 择性在内 的总碳 物料平衡 计算结果 ． 考 察了不同 Ｍｏ 担 载量对催 化剂性 能和 积炭 行为 的影响； 重点考察 了不同 温度焙烧 后２０ ％ Ｍｏ／ Ｈ Ｚ Ｒ Ｐ１ 催化剂 的性能和 积炭行 为． 在 反应的初 始阶段 ，６ ％ Ｍｏ／ Ｈ Ｚ Ｒ Ｐ１ 表 现出 很 高 的 活 性： 反 应 进 行 ３０ ｍｉｎ 时， 甲 烷 转 化 率 为 １１ ％ ， 芳 烃 选 择 性 达８１ ％ ， 而催化 剂的结焦 选择性 仅为１２ ％ ． Ｂ Ｅ Ｔ， Ｎ Ｈ３ Ｔ Ｐ Ｄ 和 催 化反 应等 表 征结 果表 明： Ｍｏ 物种的数量 和状态， 分子筛的 酸强度和 酸量以 及分子筛 的孔道 结构是 决定 甲烷 无氧 脱氢 芳构 化反 应性能和积 炭行为 的关键因 素．     

Ni80P20合金的非晶化度与催化活性的关联

采用淬冷法,通过改变冷却铜辊的转速,得到了一系列具有不同非晶化度的Ｎｉ８０Ｐ２０合金材料。以乙炔加氢为探针反应的催化研究结果表明,合金的催化活性随非晶化程度的增加而增加,同时,非晶态合金具有比相应的晶态金合明显优良的催化稳定性,ＸＲＤ和ＡＥＳ深度分析显示：在氧化－还原活化处理过程中,相对晶态合金而言,非晶态合金显示明显的“惰性”,活化后的表面上含有较多的对加氢反应有促进作用的氧化镍相互作用的结构。