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Theoretical calculation of effect of OH* on methane partial oxidation to CO on Ni(111)
- Low-carbon Chemistry and Chemical Engineering Vol. 49, Issue 11, Pages: 28-35(2024)
- 作者机构：
1.太原理工大学 化学工程与技术学院，山西 太原 030024
2.山西省超级计算中心，山西 吕梁 033015
- 作者简介：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240067
CLC： TE65Published：25 November 2024，
Received：26 February 2024，
Revised：21 March 2024，
- 稿件说明：
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陈鹏,孟园园,丁传敏等.OH*对Ni(111)上甲烷部分氧化成CO影响的理论计算[J].低碳化学与化工,2024,49(11):28-35.
CHEN Peng,MENG Yuanyuan,DING Chuanmin,et al.Theoretical calculation of effect of OH* on methane partial oxidation to CO on Ni(111)[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):28-35.
陈鹏,孟园园,丁传敏等.OH*对Ni(111)上甲烷部分氧化成CO影响的理论计算[J].低碳化学与化工,2024,49(11):28-35. DOI： 10.12434/j.issn.2097-2547.20240067.
CHEN Peng,MENG Yuanyuan,DING Chuanmin,et al.Theoretical calculation of effect of OH* on methane partial oxidation to CO on Ni(111)[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):28-35. DOI： 10.12434/j.issn.2097-2547.20240067.
摘要
为促进我国能源结构转型和缓解能源短缺压力，将储量丰富的天然气（甲烷）部分氧化成合成气具有重要的现实意义。该过程常用的催化剂为Ni基催化剂，其存在易积炭失活的问题。深入研究Ni基催化剂表面的催化机理有助于解决该问题。基于密度泛函理论的第一性原理计算方法，确定了甲烷部分氧化中相关物种在Ni(111)上最有利的吸附构型，并通过二聚体方法搜索了反应过程中各基元反应的过渡态，分析了Ni(111)上甲烷部分氧化生成CO的整个过程。结果表明，CH*在Ni(111)上的吸附能为6.98 eV，CH
2
*脱氢生成CH*的活化能为0.28 eV，远低于CH*脱氢的活化能（1.29 eV），说明CH*可在Ni表面大量存在，并且其变化可影响整个反应途径。在甲烷部分氧化生成CO的整个过程中，OH*氧化CH*生成CO*时的活化能为1.48 eV，较C*被O*直接氧化生成CO的活化能（1.59 eV）低0.11 eV，因此形成OH*更有利于CO的生成。在CH*被OH*氧化生成CO*的过程中，经历了CHOH* → COH* → CO*的转化过程，整个转化过程的活化能为0.91 eV；而CHOH* → CHO* → CO*的转化过程的活化能为0.73 eV，因此CHOH*更
倾向于脱氢生成CHO*进而生成CO*，甲烷部分氧化生成CO*的最佳反应路径为CH
4
*
→ CH
3
*
→ CH
2
*→ CH* + OH* → CHOH* → CHO* → CO*。
Abstract
In order to promote the transformation of China’s energy structure and alleviate the pressure of energy shortage
it is of great practical significance to partially oxidize natural gas (methane) with abundant reserves into syngas. The catalysts commonly used in this process is the Ni-based catalysts
which are prone to carbon deposition and inactivation. In-depth study of the catalytic mechanism on the surface of Ni-based catalysts can help to solve this problem. Based on the first-principles calculation method of density functional theory
the most favorable adsorption configuration of related species on Ni(111) in methane partial oxidation was determined
and the transition states of each element reaction in the reaction process were searched by the dimer method
and the whole process of methane partial oxidation on Ni(111) to CO was analyzed. The results show that the adsorption energy of CH* on Ni(111) is 6.98 eV
and the activation energy of CH
2
* dehydrogenation to CH* is 0.28 eV
which is much lower than that of CH* dehydrogenation (1.29 eV)
indicating that CH* can exist in large quantities on the Ni surface
and its change can affect the whole reaction pathway. In the whole process of methane partial oxidation to CO
the activation energy of CH* to CO* oxidation by OH* is 1.48 eV
which is 0.11 eV lower than that of C* direct oxidation by O* to CO (1.59 eV)
so the formation of OH* is more conducive to CO formation. In the process of oxidation of CH* by OH* to form CO*
the conversion process of CHOH* → COH* → CO* is undertaken
and the activation energy of the whole conversion process is 0.91 eV. The activation energy of the conversion procces (CHOH* → CHO* → CO*) is 0.73 eV
so CHOH* is more inclined to dehydrogenation to form CHO* and then CO*
and the optimal reaction path of
methane partial oxidation to CO* is CH
4
* → CH
3
* → CH
2
*→ CH* + OH* → CHOH* → CHO* → CO*.
关键词
OH*甲烷部分氧化Ni(111)密度泛函理论
Keywords
OH*methane partial oxidationNi(111)density functional theory
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