Reagent Triggers Isomerization of Fluxional Cluster Catalyst via Dynamic Coupling.
Reagent Triggers Isomerization of Fluxional Cluster Catalyst via Dynamic Coupling.
复制标题
试剂通过动态耦合触发流动簇催化剂的异构化。
DOI：
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发表时间：
2020
影响因子：
5.7
通讯作者：
A. Alexandrova
中科院分区：
文献类型：
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作者：
Han Guo;P. Sautet;A. Alexandrova
金属簇催化剂具有许多化学上可接近的异构体，具有不同的活性位点和低反应势垒，最近出现了一个强有力的假设，即许多催化剂状态共同驱动催化。然而，它仍然是一个假设，催化剂异构化实际上是在反应条件下动力学可行的。使用高温动力学模拟和采样的取向和振动能量分布的范围内，我们探测热效应和分子事件如何影响簇催化剂动力学。我们表明，即使是这样一个微妙的事情，作为一个解离或散射的甲烷分子上的重，因此缓慢的Pt 13集群触发大量异构化的催化剂，远远超过热在700 K。甲烷活性和簇催化剂动力学之间的动力学耦合观察。作为回报，团簇的热动力学影响甲烷反应和散射概率。因此，在流动簇催化剂的表面的分子事件，应促进人口的整体的催化剂状态在反应条件下，与可用的活性位点，反应机制，和表观速率的影响。
Metallic cluster catalysts have many thermodynamically-accessible isomers with diverse active sites and low reaction barriers, and lately a strong hypothesis emerged that the many catalysts states collectively drive the catalysis. However, it remained a hypothesis that catalyst isomerization is actually kinetically feasible in reaction conditions. Using high-temperature dynamics simulations and sampling a range of orientations and vibrational energy distributions, we probe how thermal effects and molecular events affect cluster catalyst dynamics. We show that even such a delicate affair as a dissociation or scattering of a methane molecule on the heavy and thus slow Pt13 cluster triggers substantial isomerization of the catalyst, far beyond thermal at 700 K. A kinetic coupling between the methane activity and cluster catalyst dynamics is observed. In return, the thermal dynamics of the cluster affects the methane reaction and scattering probabilities. Hence, molecular events at the surfaces of fluxional cluster catalysts should facilitate population of an ensemble of the catalyst states in reaction conditions, with implications for available active sites, reaction mechanisms, and apparent rates.
DOI：
10.1021/acs.jpclett.6b01022
发表时间：
2016-07-07
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
Nattino F;Migliorini D;Kroes GJ;Dombrowski E;High EA;Killelea DR;Utz AL
通讯作者：
Utz AL
DOI：
10.1021/acs.jpclett.7b01905
发表时间：
2017-09-07
期刊：
The journal of physical chemistry letters
影响因子：
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作者：
Migliorini D;Chadwick H;Nattino F;Gutiérrez-González A;Dombrowski E;High EA;Guo H;Utz AL;Jackson B;Beck RD;Kroes GJ
通讯作者：
Kroes GJ