Activating Graphyne Nanosheet via sp-Hybridized Boron Modulation for Electrochemical Nitrogen Fixation,Inorganic Chemistry

当前位置： X-MOL 学术 › Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Activating Graphyne Nanosheet via sp-Hybridized Boron Modulation for Electrochemical Nitrogen Fixation
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-08-22 00:00:00 , DOI: 10.1021/acs.inorgchem.9b02280
Qilong Liu ₁ , Sini Wang ₁ , Guilin Chen ₂ , Qiangchun Liu ₁ , Xiangkai Kong _{1,

3}

Affiliation

Exploring new metal-free catalysts with high activity for nitrogen reduction reaction (NRR) is highly desirable but remains a big challenge. Graphyne (GY) is a typical two-dimensional carbon material with many excellent properties. However, the NRR has rarely been envisaged on a GY-based metal-free catalyst up to now. Density functional theory calculations reveal that although pristine GY is inactive for N₂ reduction, boron modulation can endow it with efficient activity toward NRR. Natural bond orbitals analysis, spin/charge density distributions, and free energy change diagrams are performed and discussed. Three boron doping formats including sp²-substituted, sp-substituted, and adsorbed configuration are considered. The obtained data show sp-substitution will induce local moderate spin and charge densities at the boron site on the GY surface, which is convenient for N₂ adsorption and activation, and conductive to N-related intermediates formation and transformation. Moreover, the incorporated sp-hybridized boron can provide one empty p orbital and one occupied p orbital around itself, which plays a key role as an electron reservoir to accept electrons from and donate electrons to the adsorbed N-related species, and thus facilitate N₂ reduction and ammonia synthesis. Henceforth, it provides more opportunities for preparing GY and other carbon materials as efficient catalysts toward renewable energy conversion and storage.

中文翻译：

通过sp混合硼调制活化Graphyne纳米片用于电化学固氮

迫切需要开发具有高活性的氮还原反应（NRR）的新型无金属催化剂，但仍然是一个巨大的挑战。石墨烯（GY）是一种典型的二维碳材料，具有许多优异的性能。然而，到目前为止，很少有人设想在基于GY的无金属催化剂上使用NRR。密度泛函理论计算表明，尽管原始GY对于N ₂还原没有活性，但硼调制可以使其对NRR具有有效的活性。进行并讨论了自然键轨道分析，自旋/电荷密度分布和自由能变化图。三种硼掺杂格式，包括sp ²考虑了-取代，sp-取代和吸附构型。获得的数据表明，sp取代将在GY表面的硼位上引起局部适度的自旋和电荷密度，这有利于N _2的吸附和活化，并有助于N相关的中间体的形成和转化。而且，掺入的杂杂硼可以在其自身周围提供一个空的p轨道和一个被占据的p轨道，这起重要的电子储库作用，可以从被吸附的N相关物质中接受电子并将电子提供给被吸附的N相关物质，从而促进N的吸收。₂还原与氨合成。今后，它为制备GY和其他碳材料作为可再生能源转化和存储的有效催化剂提供了更多机会。

更新日期：2019-08-22

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南