MoTe2 边缘上 CO2RR 和 HER 反应机制的大规范 DFT 研究,The Journal of Physical Chemistry C

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MoTe2 边缘上 CO2RR 和 HER 反应机制的大规范 DFT 研究
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-09-18 , DOI: 10.1021/acs.jpcc.3c04474
Pernille D. Pedersen ₁ , Marko M. Melander ₂ , Thomas Bligaard ₁ , Tejs Vegge ₁ , Karoliina Honkala ₂ , Heine A. Hansen ₁

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MoTe ₂已被实验和理论上确定为电催化CO ₂还原（CO2RR）的有前途的阴极候选物。充分理解其反应性需要特别考虑反应动力学，但由于正则密度泛函理论 (DFT) 中电极电势的变化，这需要大正则、恒定电势方法，因此这是一项挑战。在这里，使用具有混合溶剂模型的大正则系综 DFT 方法，在碱性介质中的MoTe ₂边缘上研究了 CO2RR 到 CO 和竞争析氢反应 (HER) 的完整反应路径，以了解施加的电位。我们的结果表明，第一个 CO2RR 步骤的势垒，即 CO₂吸附率低于第一个 HER 步骤（Volmer 步骤），这意味着 CO2RR 受到青睐。我们还发现，在更负的电位下，第一个 CO2RR 步骤变得更有利，而 CO 解吸变得不太有利，这表明预计会进一步减少 CO，而不是 CO 解吸。_{然而，Volmer步骤的电势比CO 2}吸附更强烈地依赖于电势，使得HER在更负的电势下更有利。总的来说，我们的研究确定了边缘丰富的 MoTe ₂纳米带作为碱性 CO2RR 的可能催化剂。

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Grand Canonical DFT Investigation of the CO2RR and HER Reaction Mechanisms on MoTe2 Edges

MoTe₂ has been experimentally and theoretically identified as a promising cathode candidate for electrocatalytic CO₂ reduction (CO2RR). A full understanding of its reactivity requires special consideration of the reaction kinetics, but this is challenging due to the varying electrode potential in the canonical density functional theory (DFT), which calls for grand canonical, constant potential methods. Here, the full reaction pathways for the CO2RR to CO and the competing hydrogen evolution reaction (HER) are investigated on a MoTe₂ edge in an alkaline medium using a grand canonical ensemble DFT approach with a hybrid solvent model to understand the explicit effect of the applied potential. Our results show that the barrier of the first CO2RR step, the CO₂ adsorption, is lower than the first HER step, the Volmer step, which implies that the CO2RR is favored. We also find that at more negative potentials, the first CO2RR steps become more favorable, whereas CO desorption becomes less favorable, indicating that further CO reduction is expected instead of CO desorption. However, the potential of the Volmer step depends more strongly on the potential than CO₂ adsorption, making HER more favorable at more negative potentials. Overall, our study identified edge-rich MoTe₂ nanoribbons as possible catalysts for alkaline CO2RR.

更新日期：2023-09-18

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