VO1-4+阳离子与n-CmH2m+2 (m = 3, 5, 7)烷烃的反应性研究：氧含量和碳链长度的影响

doi:10.3866/PKU.WHXB201805231

摘要/Abstract

摘要：

本论文利用飞行时间质谱的实验方法对钒氧阳离子VO_1–4⁺与直链烷烃(n-C_mH_2m+2，m = 3, 5, 7)的反应性进行了系统研究，并且利用密度泛函理论方法对VO_1–3⁺与戊烷的反应进行了理论计算。实验结果表明，在VO⁺，VO₃⁺和VO₄⁺与n-C₅H₁₂反应中，吸附反应为主要的反应通道，同时还伴随着C―H键和C―C键的活化反应。在本实验体系中，VO⁺的反应活性要优于VO₃⁺，而VO₂⁺具有最优的反应活性，可以有效的活化烷烃的C―H键和C―C键生成较轻的烷烃和烯烃。VO₄⁺含有一个η²-O₂单元，由于VO₂⁺和η²-O₂之间的弱相互作用力，在实验中该阳离子经过一定时间的冷却碰撞后会释放η²-O₂单元，并以吸附为主要通道。尽管钒氧阳离子中氧原子的氧化态从VO⁺中的+Ⅲ增加到VO₂⁺中的+Ⅴ和VO₃⁺中的+Ⅳ，其反应性却没有逐渐增加。基于目前的反应性趋势，我们做出推测如果具有更多碳原子的直链烷烃与VO_1–4⁺反应，将会生成更轻的烷烃/烯烃片段。本文中理论计算结果与实验观测结果基本一致。同时，我们的研究可以帮助研究者们理解在凝聚相催化剂表面发生的微观反应过程，从而建立更为完善的催化反应机理。

关键词: 质谱, 钒氧阳离子, 烷烃, 密度泛函理论, 反应机理

Abstract:

Vanadium oxides are one of the most important heterogeneous catalysts that are widely used to oxidize hydrocarbon molecules into value-added chemicals. In order to reveal the mechanisms and the nature of active sites, numerous experimental and theoretical studies have been reported on the reactivities of gas-phase vanadium oxide clusters toward small molecules. However, there has been very limited research on the chemical reactivity changes associated with the oxygen contents of vanadium oxides and the carbon chain lengths of alkanes. In this work, the reactions of vanadium oxide ions VO₁₋₄⁺ with alkanes (n-C_mH_2m+2, m = 3, 5, 7) were systematically investigated by time-of-flight mass spectrometry and the reactions of VO₁₋₃⁺ with pentane were further studied by density functional theory calculations. Experimental results show that in the reactions of VO⁺, VO₃⁺, and VO₄⁺ with n-C₅H₁₂, in addition to the major adsorption processes, the activation of the C―H and C―C bonds of n-C₅H₁₂ was observed. The activation of both the bonds was observed experimentally during the reaction of VO₂⁺ with n-C₅H₁₂ with large branching ratios. Among the vanadium oxide cations studied, VO₂⁺ shows the strongest oxidizability and the generation of lighter alkanes and alkenes dominates the reactions; VO⁺ is more reactive than VO₃⁺. VO₄⁺ pocesses only one η²-O₂ unit. Due to the weak bond between VO₂⁺ and η²-O₂, the η²-O₂ unit is released in VO₄⁺/n-C₅H₁₂ system leading to the formation of VO₂⁺; thus VO₄⁺ cations reflect some reactivity of VO₂⁺. Although the oxidation states in the vanadium oxide clusters increase from +Ⅲ in VO⁺ to +Ⅴ in VO₂⁺ and +Ⅳ in VO₃⁺, the reactivity does not gradually increase. Moreover, the reactivity of the mononuclear vanadium oxide cations also does not exhibit a gradually increasing trend with the increase in oxygen content. Based on the observed reactivity trend, the adsorption channels gradually become weak as the carbon chain lengths increase; meanwhile, the dehydrogenation and C―C bond activation channels gradually become obvious and some oxygen transfer products appear. Therefore, much lighter fragments of alkanes/alkenes will be obtained if linear alkanes with more carbon atoms were reacted with VO₁₋₄⁺. The theoretical results are generally consistent with those obtained from the experiments. The various reaction channels and versatile reactivity of the mononuclear vanadium oxide cations investigated in this study not only offer new insights into gas-phase reactions but also shed light on the processes occurring on the surfaces of the corresponding condensed-phase catalysts.

Key words: Mass spectrometry, Vanadium oxide cations, Alkanes, Density functional theory, Reaction mechanism

MSC2000:

O643

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赵越,崔佳桐,胡继闯,马嘉璧. VO_1-4⁺阳离子与n-C_mH_2m+2 (m = 3, 5, 7)烷烃的反应性研究：氧含量和碳链长度的影响[J]. 物理化学学报, 2019, 35(5): 531-538.

Yue ZHAO,Jiatong CUI,Jichuang HU,Jiabi MA. Reactivities of VO_1–4⁺ Toward n-C_mH_2m+2 (m = 3, 5, 7) as Functions of Oxygen Content and Carbon Chain Length[J]. Acta Phys. -Chim. Sin., 2019, 35(5): 531-538.

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