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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Ethanol decomposition on a Pd(110) surface: A density functional theory investigation
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Ethanol decomposition on a Pd(110) surface: A density functional theory investigation

机译：Pd（110）表面上的乙醇分解：密度泛函理论研究

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Ethanol decomposition on Pd(110) is comprehensively investigated using self-consistent periodic density functional theory. Geometries and energies for all the intermediates involved are analyzed, and the decomposition network is mapped out to illustrate the reaction mechanism. On Pd(110), the most stable adsorption of the involved species tends to follow the gas-phase bond order rules, wherein C is tetravalent and O is divalent with the missing H atoms replaced by metal atoms. The most likely decomposition pathway of ethanol on Pd(110) is CH_3CH_2OH → CH3CH2O → CH3CHO → CH_3CO → CH_3 + CO → CO + H + CH_4 + C, in which the initial dehydrogenation is the rate-limited step. No C-O scission pathway is identified. Comparing with ethanol decomposition on Pd(111) [Langmuir, 2010, 26, 1879-1888], Pd(110) characterizes relatively high activity and different selectivity. Two crucial factors controlling the variations of reactivity and selectivity from Pd(111) to Pd(110), i.e., the local electronic effect of the metals and the geometrical effect of the relevant transition states, are identified. Four distinct Br?nsted-Evans-Polanyi (BEP) relations are identified for the three types of bond scission (C-H, C-O, and C-C) if we consider Pd(111) and Pd(110) as a whole, one for C-H bond scission, one for C-O bond scission, and two for C-C bond scission.
机译：使用自洽周期密度泛函理论全面研究了Pd（110）上的乙醇分解。分析了所涉及的所有中间体的几何形状和能量，并绘制了分解网络以说明反应机理。在Pd（110）上，所涉及物质的最稳定吸附趋于遵循气相键序规则，其中C为四价，O为二价，缺失的H原子被金属原子取代。乙醇在Pd（110）上最可能的分解途径是CH_3CH_2OH→CH3CH2O→CH3CHO→CH_3CO→CH_3 + CO→CO + H + CH_4 + C，其中初始脱氢是限速步骤。没有发现C-O分裂途径。与乙醇在Pd（111）上的分解相比[Langmuir，2010，26，1879-1888]，Pd（110）具有较高的活性和不同的选择性。确定了控制反应性和选择性从Pd（111）到Pd（110）变化的两个关键因素，即金属的局部电子效应和相关过渡态的几何效应。如果我们将Pd（111）和Pd（110）整体考虑在内，则针对三种类型的键断裂（CH，CO和CC）确定了四种截然不同的Br？nsted-Evans-Polanyi（BEP）关系。断裂，一个用于CO键断裂，而两个用于CC键断裂。

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