Ammonia Synthesis Using Single-Atom Catalysts Based on Two-Dimensional Organometallic Metal Phthalocyanine Monolayers under Ambient Conditions,ACS Applied Materials & Interfaces

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Ammonia Synthesis Using Single-Atom Catalysts Based on Two-Dimensional Organometallic Metal Phthalocyanine Monolayers under Ambient Conditions
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-12-29 , DOI: 10.1021/acsami.0c18472
Chun-Xiang Huang _{1,

2} , Guoliang Li ₁ , Li-Ming Yang ₂ , Eric Ganz ₃

Affiliation

We have identified three novel metal phthalocyanine (MPc, M = Mo, Re, and Tc) single-atom catalyst candidates with excellent predicted performance for the production of ammonia from electrocatalytic nitrogen reduction reaction (NRR) through a combination of high-throughput screening and first-principles calculations on a series of 3d, 4d, and 5d transition metals anchored onto extended Pc monolayer catalysts. Analysis of the energy band structures and projected density of states of N₂-MPc revealed significant orbital hybridization and charge transfer between the adsorbed N₂ and catalyst MPc, which accounts for the high catalytic activity. Among 30 MPc catalysts, MoPc and TcPc monolayers were found to be the most promising new NRR catalysts, as they exhibit excellent stability, low onset potential, and high selectivity. A comprehensive reaction pathway search found that the maximum free energy changes for the MoPc and TcPc monolayers are 0.33 and 0.54 eV, respectively. As a distinctive nature of this work, the hybrid reaction pathway was considered extensively and searched systematically. The onset potential of the hybrid pathway is found to be smaller than or comparable to that of the commonly known pure pathway. Thus, the hybrid path is highly competitive with low onset potential and high activity. The hybrid pathway is expected to have an important impact on future research on the mechanism of NRR, and it will open up a new way to explore the mechanism of the NRR reaction. We hope that our work will provide impetus to the creation of new catalysts for reduction of N₂ to NH₃. This work provides new insights into the rational design of NRR catalysts and explores novel reaction pathways under ambient or mild conditions.

中文翻译：

二维有机金属金属酞菁单分子膜在环境条件下用单原子催化合成氨

我们已经确定了三种新颖的金属酞菁（MPc，M = Mo，Re和Tc）单原子催化剂候选物，这些候选物具有通过高通量筛选和高通量筛选与电催化氮还原反应（NRR）合成氨的优异预测性能。对固定在扩展的Pc单层催化剂上的一系列3d，4d和5d过渡金属的第一性原理计算。对N ₂ -MPc的能带结构和状态的预计密度的分析表明，明显的轨道杂化和吸附的N ₂之间的电荷转移催化剂MPc，具有高催化活性。在30种MPc催化剂中，发现MoPc和TcPc单层膜是最有希望的新型NRR催化剂，因为它们表现出出色的稳定性，低起始电位和高选择性。全面的反应途径搜索发现，MoPc和TcPc单层的最大自由能变化分别为0.33和0.54 eV。作为这项工作的独特性质，人们广泛地考虑了杂化反应途径并对其进行了系统地研究。发现杂化途径的发作潜力小于或与通常已知的纯途径的发作潜力相当。因此，混合路径竞争激烈，具有低发作潜力和高活性。混合路径有望对NRR机制的未来研究产生重要影响，这将为探索NRR反应机理开辟新途径。我们希望我们的工作将为创造减少氮含量的新催化剂提供动力。₂至NH ₃。这项工作为NRR催化剂的合理设计提供了新的见识，并探索了在环境或温和条件下的新颖反应途径。

更新日期：2021-01-13

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