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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Nitric Oxide Adsorption and Reduction Reaction Mechanism on the Rh_7~+ Cluster: A Density Functional Theory Study
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Nitric Oxide Adsorption and Reduction Reaction Mechanism on the Rh_7~+ Cluster: A Density Functional Theory Study

机译:一氧化氮在Rh_7〜+团簇上的吸附和还原反应机理:密度泛函理论研究

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The transition metal rhodium has been proved the effective catalyst to convert from NO_x to N_2. In the present work, we are mainly focused on the NO adsorption and decomposition reaction mechanism on the surface of the Rh_7~+ cluster, and the calculated results suggest that the reaction can proceed via three steps. First, the NO can adsorb on the surface of the Rh_7~+ cluster; second, theNOdecomposes toNandOatoms; finally, theNatom reacts with the second adsorbed NO and reduces to a N_2 molecule. The N-O bond breaks to yield N and O atoms in the second step, which is the rate-limiting step of the whole catalytic cycle. This step goes over a relatively high barrier (TS_(12)) of 39.6 kcal/mol and is strongly driven by a large exothermicity of 55.1 kcal/mol during the formation of stable compound 3, accompanied by the N and O atoms dispersed on the different Rh atoms of the Rh_7~+ cluster. In addition, the last step is very complex due to the different possibilities of reaction mechanism. On the basis of the calculations, in contrast to the reaction path II that generates N_2 from two nitrogen atoms coupling, the reaction path I for the formation of intermediate N_2O is found to be energetically more favorable. Present work would provide some valuable fundamental insights into the behavior of the nitric oxide adsorption and reduction reaction mechanism on the Rh_7~+ cluster.
机译:过渡金属铑已被证明是将NO_x转化为N_2的有效催化剂。在目前的工作中,我们主要集中在Rh_7〜+团簇表面的NO吸附和分解反应机理,计算结果表明该反应可以通过三个步骤进行。首先,NO可以吸附在Rh_7〜+团簇的表面。第二,NO分解为NandOatoms;最终,Natom与第二个吸附的NO反应,还原为N_2分子。在第二步中,N-O键断裂,生成N和O原子,这是整个催化循环的限速步骤。该步骤超过了39.6 kcal / mol的相对较高的势垒(TS_(12)),并在形成稳定化合物3的过程中受到55.1 kcal / mol的大放热的强烈推动,同时伴随着N和O原子的分散。 Rh_7〜+团簇的不同Rh原子。另外,由于反应机理的不同可能性,最后一步非常复杂。根据计算,与从两个氮原子偶合生成N_2的反应路径II相反,发现用于形成中间体N_2O的反应路径I在能量上更有利。目前的工作将为一氧化氮在Rh_7〜+团簇上的吸附和还原反应机理的行为提供一些有价值的基础见解。

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