Heterogeneous Two-Atom Single-Cluster Catalysts for the Nitrogen Electroreduction Reaction,The Journal of Physical Chemistry C

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Heterogeneous Two-Atom Single-Cluster Catalysts for the Nitrogen Electroreduction Reaction
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2021-09-01 , DOI: 10.1021/acs.jpcc.1c06339
Jun-Chi Chen ₁ , Hao Cao ₁ , Jie-Wei Chen ₁ , Sheng-Jie Qian ₁ , Guang-Jie Xia ₁ , Yang-Gang Wang ₁ , Jun Li _{1,

2}

Affiliation

The electrocatalytic dinitrogen reduction reaction (NRR) is promising to realize the decentralized production of ammonia by using renewable energies, which contrasts with the energy-intensive Haber–Bosch process. The key to achieve it is to find stable, efficient and selective catalysts. Recently, the heterogeneous single-cluster catalysts (SCCs) have emerged as a promising class of catalysts for electrochemical reactions due to their atomically precise active site, abundant active atoms and atomic level controllability. Herein, the NRR catalyzed by the two-atom SCCs consisting of homonuclear 3d transition metal (TM) dimers over the N-doped graphene, denoted as M₂-N₆G, is systematically investigated by using density functional theory (DFT). Our results indicate that the ability of metal dimer to capture N₂ is related to the reducibility of the catalyst and the orbital interaction between the N-2p states and the TM-3d states. Subsequently, comparing with those metals which overbind N₂ through side-on configurations, the M₂-N₆G SCCs with end-on adsorption of N₂ work better. Furthermore, we obtain a linear relationship between the adsorption free energies of *N₂H (Δ_adsG_*NH₂) and that of *NH₂ (Δ_adsG_*NH₂). Based on this scaling relationship, we propose a compromised strategy for screening efficient two-atom SCCs for NRR. Finally, by comparing the stability, activity and selectivity of various M₂-N₆G SCCs, the Cr₂-N₆G and Mn₂-N₆G are predicted to be most active for NRR with low limiting potential and high suppression to hydrogen evolution reaction (HER). The present work not only provides experimentally synthesizable electrocatalyst candidates for NRR, but also gives insight into the development of the two-atom SCCs.

中文翻译：

用于氮电还原反应的多相双原子单簇催化剂

电催化二氮还原反应（NRR）有望通过使用可再生能源实现氨的分散生产，这与能源密集型的哈伯-博世工艺形成鲜明对比。实现它的关键是找到稳定、高效和选择性的催化剂。最近，非均相单簇催化剂（SCC）由于其原子级精确的活性位点、丰富的活性原子和原子级可控性而成为一类有前途的电化学反应催化剂。在本文中，由 N 掺杂石墨烯上的同核 3d 过渡金属 (TM) 二聚体组成的双原子 SCC 催化 NRR，表示为 M ₂ -N ₆G, 是通过使用密度泛函理论 (DFT) 系统地研究的。我们的结果表明，金属二聚体捕获 N ₂的能力与催化剂的还原性以及 N-2p 态和 TM-3d 态之间的轨道相互作用有关。接着，利用该overbindÑ这些金属相比较₂通过侧上的配置，所述M _2倍-N _6倍ģ的SCC与最终在N个的吸附₂更好地工作。此外，我们得到* N的吸附自由能之间的线性关系₂ H（Δ_广告ģ _{* NH ₂}）和的NH * ₂（Δ_广告ģ _{* NH ₂}）。基于这种缩放关系，我们提出了一种折衷策略，用于筛选 NRR 的有效双原子 SCC。最后，通过比较各种 M ₂ -N ₆ G SCC的稳定性、活性和选择性，预测Cr ₂ -N ₆ G 和 Mn ₂ -N ₆ G 对 NRR 最活跃，具有低限制电位和高抑制析氢反应 (HER)。目前的工作不仅为 NRR 提供了可实验合成的电催化剂候选者，而且还深入了解了双原子 SCC 的发展。

更新日期：2021-09-16

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