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Origin of Confined Catalysis in Nanoscale Reactors between Two-Dimensional Covers and Metal Substrates: Mechanical or Electronic?
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-05-05 , DOI: 10.1021/acs.jpcc.0c03621
Fenfei Wei 1 , Qiang Wan 1 , Sen Lin 1 , Hua Guo 2
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-05-05 , DOI: 10.1021/acs.jpcc.0c03621
Fenfei Wei 1 , Qiang Wan 1 , Sen Lin 1 , Hua Guo 2
Affiliation
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The origin of confined catalysis in well-defined nanoscale reactors between two-dimensional (2D) covers and underlying substrates is often attributed to a confinement-induced weakening of the interaction between the confined reactants and substrate due to mechanical forces. However, the energetics of the species along the reaction path can also be perturbed by electronic factors such as charge transfer, thus changing the kinetics and thermochemistry of the reaction. This electronic mechanism has seldom been considered. Here, we investigate the dissociation of methane in a nanoscale reactor between a 2D cover (graphene or hexagonal boron nitride) and a metal surface (Cu, Pt, or Ni) using dispersion-corrected density functional theory. The dissociation of H2O and NH3 in the confined space between the 2D cover and Pt surface is also explored. Our results indicate that the reactivity can be affected not only by a mechanical effect induced by the geometric constraint but also by electronic effects due to charge transfer. For CH4* → CH3* + H*, for example, the mechanical effect is dominant while the electronic effect is negligible. For H2O* → OH* + H*, on the other hand, the electronic effect plays a major role in reducing the energy barrier, but the mechanical effect is negligible. For NH3* → NH2* + H*, both effects are minor, and the confinement is ineffective. Our results offer new insight into the origin of confined catalysis, which can help design high-performance nanoscale reactors.
中文翻译：
二维覆盖物和金属基材之间的纳米级反应器中受限催化的起源：机械还是电子？
二维（2D）覆盖层和下层基材之间定义明确的纳米反应器中受限催化的起源通常归因于受限诱导的由于机械力而导致的受限反应物与基材之间相互作用的减弱。但是，沿着电子路径的物质的高能也可能会受到电子因素（例如电荷转移）的干扰，从而改变了反应的动力学和热化学性质。很少考虑这种电子机制。在这里，我们使用分散校正的密度泛函理论研究了纳米反应器中2D覆盖层（石墨烯或六方氮化硼）与金属表面（Cu，Pt或Ni）之间甲烷的解离。H 2 O和NH 3的离解在2D覆盖层和Pt表面之间的密闭空间中也进行了探索。我们的结果表明，反应性不仅受几何约束引起的机械效应的影响，还受电荷转移引起的电子效应的影响。例如，对于CH 4 *→CH 3 * + H *，机械效应占主导，而电子效应则可以忽略。另一方面，对于H 2 O *→OH * + H *，电子效应在减小能垒中起主要作用，但机械效应可忽略不计。对于NH 3 *→NH 2* + H *，两者的影响均较小，并且限制无效。我们的结果为限制催化的起源提供了新的见解，可以帮助设计高性能纳米级反应器。
更新日期：2020-05-05
中文翻译：
二维覆盖物和金属基材之间的纳米级反应器中受限催化的起源：机械还是电子？
二维（2D）覆盖层和下层基材之间定义明确的纳米反应器中受限催化的起源通常归因于受限诱导的由于机械力而导致的受限反应物与基材之间相互作用的减弱。但是，沿着电子路径的物质的高能也可能会受到电子因素（例如电荷转移）的干扰，从而改变了反应的动力学和热化学性质。很少考虑这种电子机制。在这里，我们使用分散校正的密度泛函理论研究了纳米反应器中2D覆盖层（石墨烯或六方氮化硼）与金属表面（Cu，Pt或Ni）之间甲烷的解离。H 2 O和NH 3的离解在2D覆盖层和Pt表面之间的密闭空间中也进行了探索。我们的结果表明，反应性不仅受几何约束引起的机械效应的影响，还受电荷转移引起的电子效应的影响。例如，对于CH 4 *→CH 3 * + H *，机械效应占主导，而电子效应则可以忽略。另一方面，对于H 2 O *→OH * + H *，电子效应在减小能垒中起主要作用，但机械效应可忽略不计。对于NH 3 *→NH 2* + H *，两者的影响均较小，并且限制无效。我们的结果为限制催化的起源提供了新的见解，可以帮助设计高性能纳米级反应器。
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