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DENSITY FUNCTIONAL STUDY OF NO DESORPTION FROM OXIDATION OF NITROGEN CONTAINING CHAR BY O_2

机译:O_2氧化含氮煤焦中NO脱附的密度泛函研究。

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摘要

Mechanisms for NO desorption during reactions between O_2 and nitrogen-containing char have been studied using density functional theory at the B3L YPI6-3IG(d) level. The chemi-sorption of O_2 on char surface was found to be barrierless and 440 kJmol~(-1) exothermic. A number of reaction pathways with barriers below 440kJmol~(-1) were characterized. The chemisorption product could proceed directly to NO desorption with an energy barrier of 419kJmol~(-1) or undergo a series of rearrangement reactions to release NO, in which the highest energy barrier was 360kJmol~(-1) . An oxygen atom could migrate along the edge of char if an adjacent active site was vacant. The overall migration reaction was 107 kJmol~(-1) exothermic. Transition state theory was used to calculate forward and reverse rate constants of intermediate reactions in the range of 1000-1800 K and two-parameter Arrhenius expressions were fitted. NO formation from nitrogen-containing char heterogeneous oxidation was dominated by indirect pathway consisting of a series of rearrangement reactions.
机译:利用密度泛函理论在B3L YPI6-3IG(d)水平上研究了O_2与含氮焦炭反应过程中NO脱附的机理。发现O_2在焦炭表面的化学吸附是无障碍的,并且放热为440 kJmol〜(-1)。表征了多种势垒低于440kJmol〜(-1)的反应途径。化学吸附产物可以以419kJmol〜(-1)的能垒直接进行NO的解吸或发生一系列重排反应以释放NO,其中最高的能量垒为360kJmol〜(-1)。如果相邻的活性位点是空的,则氧原子可沿炭的边缘迁移。总迁移反应是放热的107 kJmol〜(-1)。过渡态理论用于计算1000-1800 K范围内中间反应的正向和反向速率常数,并拟合了两参数Arrhenius表达式。由含氮的碳异质氧化形成的NO受到一系列一系列重排反应的间接途径的支配。

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  • 来源
    《Combustion Science and Technology》 |2012年第6期|p.445-455|共11页
  • 作者单位

    State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, Zhejiang, China;

    State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Zheda Road 38#, Hangzhou 310027,Zhejiang, China;

    State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, Zhejiang, China;

    State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, Zhejiang, China;

    State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, Zhejiang, China;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    density functional theory; heterogeneous reaction mechanism; nitric oxide; nitrogen-containing char;

    机译:密度泛函理论;异质反应机理一氧化氮;含氮焦炭;

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