Boosting Electrocatalytic N2 Reduction to NH3 over Two-Dimensional Gallium Selenide by Defect-Size Engineering,Inorganic Chemistry

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Boosting Electrocatalytic N2 Reduction to NH3 over Two-Dimensional Gallium Selenide by Defect-Size Engineering
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-03-18 , DOI: 10.1021/acs.inorgchem.0c00131
Mengyuan Li ₁ , Yu Cui ₁ , Liping Sun ₁ , Xiaoli Zhang ₁ , Lei Peng ₁ , Yucheng Huang ₁

Affiliation

Using density functional theory calculations, we propose that the exposed Ga atom in a two-dimensional defective gallium selenide monolayer (V-GaSe) can display a good dinitrogen fixation capacity and an excellent nitrogen reduction reaction (NRR) performance. Our results show that N₂ can be captured by three sp³-hybridized Ga atoms due to the pulling effect. With the enlargement in vacancy size through applying tensile strain, the adsorption of N₂ is strengthened and the electrochemical NRR performance is enhanced. On 8% strained V-GaSe, the estimated onset potential is as low as 0.30 V. Inspired by the concept of “defect-size-dependent” NRR performance, we further design a Janus V-GaInSe₂ structure in which the natural size of the cavity is enlarged and the electron density of the active Ga atoms is enriched. It is found that N₂ adsorption is demonstrably enhanced with respect to V-GaSe. On 4% strained V-GaInSe₂, the onset potential is calculated to be 0.31 V, which is the same as the 8% strained V-GaSe. Moreover, the produced NH₃ can be removed rapidly with a free-energy change of less than 0.52 eV, which is much lower than those of most reported catalysts with low overpotentials. Meanwhile, the side hydrogen evolution reaction is successively suppressed as the strain increases. Our work offers a feasible method that utilizes the size of a defect to tune the NRR performance, adding a new understanding of N₂ fixation and sustainable NH₃ production.

中文翻译：

缺陷尺寸工程在二维硒化镓上促进电催化N ₂还原为NH ₃

使用密度泛函理论计算，我们建议二维缺陷硒化镓单层（V-GaSe）中暴露的Ga原子可以表现出良好的固氮能力和出色的氮还原反应（NRR）性能。我们的结果表明，由于拉动效应，N ₂可以被三个sp ^3-杂化的Ga原子捕获。通过施加拉伸应变，随着空位尺寸的增大，N ₂的吸附增强，电化学NRR性能增强。在8％应变的V-GaSe上，估计的起始电势低至0.30V。受“取决于缺陷大小”的NRR性能概念的启发，我们进一步设计了Janus V-GaInSe ₂该结构的空腔的自然尺寸增大了，而活性Ga原子的电子密度得到了丰富。已经发现，相对于V-GaSe ，N ₂吸附被明显增强。在4％应变的V-GaInSe _2上，计算出的起始电势为0.31 V，与8％应变的V-GaSe相同。此外，所产生的NH ₃可以以小于0.52 eV的自由能变化快速除去，这比大多数报道的低超电势催化剂要低得多。同时，随着应变的增加，侧向析氢反应被依次抑制。我们的工作提供了一种可行的方法，该方法利用缺陷的大小来调整NRR性能，从而对N ₂有了新的认识。固定和可持续的NH ₃生产。

更新日期：2020-03-19

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