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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >DFT Study on the Catalytic Activity of ALD-Grown Diiron Oxide Nanoclusters for Partial Oxidation of Methane to Methanol
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DFT Study on the Catalytic Activity of ALD-Grown Diiron Oxide Nanoclusters for Partial Oxidation of Methane to Methanol

机译：ALD生长二氧化物氧化物纳米能催化活性的DFT研究甲烷部分氧化甲醇

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摘要

Using density functional theory (DFT), we studied the catalytic activity of iron oxide nanoclusters that mimic the structure of the active site in the soluble form of methane monooxygenase (sMMO) for the partial oxidation of methane to methanol. Using N2O as the oxidant, we consider a radical-rebound mechanism and a concerted mechanism for the oxidation of methane on either a bridging oxygen (O-b) or a terminal oxygen (O-t) active site. We find that the radical-rebound pathway is preferred over the concerted pathway by 40-50 kJ/mol, but the desorption of methanol and the regeneration of the oxygen site are found to be the highest barriers for the direct conversion of methane to methanol with these catalysts. As demonstrated by a population analysis, the O-x (x = b or t) site behaves as an oxygen radical during the H abstraction, and the [Fe+-O-x(-)] site behaves as a Lewis acid-base pair during the concerted C-H cleavage. Molecular orbital decomposition analysis further demonstrates electron transfer during the oxidation and reduction steps of the reaction. High-level multireference calculations were also carried out to further assess the DFT results. Understanding how these systems behave during the proposed reaction pathways provides new insights into how they can be tuned for methane partial oxidation.
机译：使用密度函数理论（DFT），我们研究了氧化铁纳米能器的催化活性，其以可溶性形式的甲烷单氧基酶（SMMO）的活性位点的结构用于将甲烷部分氧化成甲醇。使用N2O作为氧化剂，我们考虑一种自由基回弹机构和用于在桥接氧（O-B）或末端氧（O-T）活性位点上的甲烷氧化的齐齐因力机制。我们发现，通过40-50kJ / mol的协调途径优选自由基回弹途径，但甲醇的解吸和氧气部位的再生是最高的甲烷与甲醇的最高障碍这些催化剂。如人口分析所证明，氧（X = B或T）位点在H抽象期间表现为氧自由基，并且[Fe + -ox（ - ）]现场在齐全的CH期间表现为Lewis酸碱对乳沟。分子轨道分解分析进一步证明了在反应的氧化和还原步骤期间的电子转移。还进行了高级多推导计算，以进一步评估DFT结果。了解这些系统在所提出的反应途径期间如何表现如何为如何调整甲烷部分氧化的新见解。

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