| Ni的化学态对甲烷部分氧化反应机理的影响: 能学分析 |
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| 引用本文： | 夏文生,常刚,侯玉慧,翁维正,万惠霖.Ni的化学态对甲烷部分氧化反应机理的影响: 能学分析[J].物理化学学报,2011,27(7):1567-1573. |
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| 作者姓名： | 夏文生 常刚 侯玉慧 翁维正 万惠霖 |
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| 作者单位： | State Key Laboratory of Physical Chemistry for Solid State Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Fujian Province Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China |
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| 基金项目： | China，National Key Basic Research Program of China(973)(2010CB732303).国家自然科学基金，福建省自然科学基金，国家重点基础研究发展规划项目(973) |
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| 摘 要： | 采用键指数归一-平方势(UBI-QEP)法对不同化学态Ni上甲烷部分氧化反应中各可能基元步骤进行了能学计算研究. 结果表明, 反应的速度控制步骤与金属Ni的化学态有关. 还原态Ni上CO形成的反应速度控制步骤为表面上CH3与O物种间的缔合, 而带部分正电荷的Ni上CO形成的反应速度控制步骤则为甲烷氧助解离形成表面CHxO物种. 还原态和带部分正电荷的Ni中心在表面上共存时, 反应的速度控制步骤将取决于表面CH3形成与表面CH3、O物种缔合两反应间的竞争, 其竞争的强弱涉及Ni的化学态. 此外, 反应活性中心向正电荷的Ni转化时, 会导致表面C和O及H和H物种缔合的活化能显著降低, 有利于CO、H2的形成, 而表面CHx物种解离则变得不容易, 表面积炭受到明显的抑制.
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| 关 键 词： | 甲烷部分氧化 镍 化学态 速度控制步骤 机理 能量学 |
| 收稿时间： | 2011-04-01 |
| 修稿时间： | 2011-05-06 |
Influence of Ni Chemical States on the Partial Oxidation Mechanism of Methane: An Energetics Analysis |
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| XIA Wen-Sheng,CHANG Gang,HOU Yu-Hui,WENG Wei-Zheng,WAN Hui-Lin.Influence of Ni Chemical States on the Partial Oxidation Mechanism of Methane: An Energetics Analysis[J].Acta Physico-Chimica Sinica,2011,27(7):1567-1573. |
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| Authors: | XIA Wen-Sheng CHANG Gang HOU Yu-Hui WENG Wei-Zheng WAN Hui-Lin |
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| Institution: | State Key Laboratory of Physical Chemistry for Solid State Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Fujian Province Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China |
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| Abstract: | An energetics analysis of the possible elementary steps involved in the partial oxidation of methane(POM) over different chemical states of Ni was carried out using the unity bond index-quadratic exponential potential(UBI-QEP) method.The results show that the rate determining step for the partial oxidation mechanism of methane is related to the chemical state of the Ni.Over reduced Ni the rate determining step for CO formation is the association of surface CH_3 species with surface 0 species.Over a partial ... |
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| Keywords: | Partial oxidation of methane Nickel Chemical state Rate determining step Mechanism Energetics |
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