Partial Oxidation of Methane on Anatase and Rutile Defective TiO2 Supported Rh4 Cluster: A Density Functional Theory Study,The Journal of Physical Chemistry C

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Partial Oxidation of Methane on Anatase and Rutile Defective TiO2 Supported Rh4 Cluster: A Density Functional Theory Study
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/acs.jpcc.7b07489
Dan Guo ₁ , Gui-Chang Wang _{1,

2}

Affiliation

We have studied the effect of CH₄ dissociation and partial oxidation on carbon deposition resistance on oxygen-defective anatase TiO₂ supported Rh (Rh₄/Ana-Ov) and rutile TiO₂ supported Rh (Rh₄/Rut-Ov) by the density functional theory. We computed the adsorption structure of CH_x species, and the adsorption of CH_x species on Rh₄/Rut-Ov was stronger than that on Rh₄/Ana-Ov. On the Rh₄/Ana-Ov surface, the activation energy barrier of C–H bond cleavage involved in methane decomposition was higher than that on Rh₄/Rut-Ov, which means the Rh₄/Ana-Ov was favored to carbon deposition resistance. Additionally, the dominant process of methane partial oxidation was CH₂*+O* → CH₂O*, where the energy barrier on Rh₄/Ana-Ov is lower relative to Rh₄/Rut-Ov. This implies that the oxidation reaction was also favorable to the carbon deposition resistance on Rh₄/Ana-Ov. As the strong carbon deposition resistance effect on Rh₄/Ana-Ov, a high activity for syngas formation can be expected. The energetic span model analysis showed that the apparent activation energy was beneficial to the partial oxidation of methane on Rh₄/Ana-Ov compared to that of Rh₄/Rut-Ov. Moreover, the selectivity of CO was high and up to 90% by using the microkinetic model analysis, which was consistent with the experimental results. The present work may help people to design an efficient catalysts for methane partial oxidation in which there is a strong interaction with support in order to reduce the carbon deposition.

中文翻译：

锐钛矿和金红石缺陷型TiO ₂负载的Rh ₄团簇上甲烷的部分氧化：密度泛函理论研究

我们通过密度研究了CH _4的解离和部分氧化对氧缺陷型锐钛矿型TiO ₂负载的Rh（Rh ₄ / Ana-Ov）和金红石型TiO ₂负载的Rh（Rh ₄ / Rut-Ov）的碳沉积阻力的影响。功能理论。我们计算CH的吸附结构_X物种，和CH的吸附_X上的Rh物种₄ /车辙-OV比在Rh更强₄ /安娜-OV。在Rh ₄ / Ana-Ov表面，甲烷分解涉及的CH键断裂的活化能垒高于Rh ₄ / Rut-Ov，这意味着Rh ₄/ Ana-Ov有利于抗碳沉积。另外，甲烷部分氧化的主要过程是CH ₂ * + O *→CH ₂ O *，其中Rh ₄ / Ana-Ov上的能垒相对于Rh ₄ / Rut-Ov较低。这意味着氧化反应也有利于Rh ₄ / Ana-Ov上的碳沉积阻力。由于对Rh ₄ / Ana-Ov具有很强的抗碳沉积作用，因此可以期待高活性的合成气形成。中的高能跨度模型分析表明，表观活化能是甲烷在Rh部分氧化有益₄ /安娜-OV相比，Rh中的₄/ Rut-Ov。此外，通过微动力学模型分析，CO的选择性很高，高达90％，与实验结果一致。目前的工作可能会帮助人们设计出一种有效的甲烷部分氧化催化剂，该催化剂与载体之间具有很强的相互作用，以减少碳的沉积。

更新日期：2017-11-16

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