论文标题
过渡金属 - 四甲苯二甲烷单层作为电催化氮还原反应的单原子催化剂
Transition Metal-Tetracyanoquinodimethane Monolayers as Single-Atom Catalysts for Electrocatalytic Nitrogen Reduction Reaction
论文作者
论文摘要
将土壤丰富的二氮转化为增值化学氨是一个重要但充满挑战的话题。与常规的Haber-Bosch工艺相比，电催化氮还原反应（NRR）是一种节能且环保的方法。电催化NRR的主要任务是找到可以有效激活二氮并表现出高选择性和稳定性的电催化剂。单原子催化剂可以作为一个很好的解决方案。在这项工作中，通过第一原理密度功能理论，分子动力学计算以及两步筛选过程，我们确认在四苯乙甲烷二甲烷单层支持的单SC和TI原子（SC，TI-TCNQ）是NRR电载体的出色候选者。 N2吸附和激活由于接受性抑制机制和TM-TCNQ的出色电子结构而有效，而Gibbs自由能图表明，SC-TCNQ和TI-TCNQ分别通过酶促连续的混合路径表现出较低的NRR ORIPTIANTAL较低的NRR超电势为0.33和0.22 V。此外，对她的选择性以及SC/Ti-TCNQ单层的稳定性也得到了验证。这项工作开辟了一种新的途径，用于设计用于NRR以及其他催化应用的新型单原子催化剂。
Converting earth-abundant dinitrogen into value-added chemical ammonia is a significant yet challenging topic. Electrocatalytic nitrogen reduction reaction (NRR), compared with conventional Haber-Bosch process, is an energy-saving and environmentally friendly approach. The major task of electrocatalytic NRR is to find electrocatalysts which can activate dinitrogen effectively and exhibit high selectivity and stability. Single atom catalysts can act as a good solution. In this work, by means of first-principles density functional theory, molecular dynamics calculations, and a two-step screening process, we confirm that single Sc and Ti atom supported on tetracyanoquinodimethane monolayers (Sc,Ti-TCNQ) are excellent candidates for NRR electrocatalysts. N2 adsorption and activation are effective due to the acceptance-donation mechanism and outstanding electronic structure of TM-TCNQ, and Gibbs free energy diagram shows that Sc-TCNQ and Ti-TCNQ exhibit low NRR overpotential of 0.33 and 0.22 V through enzymatic-consecutive mixed pathway, respectively. In addition, selectivity over HER and stability of Sc/Ti-TCNQ monolayers are also validated. This work opens a new avenue for designing novel single atom catalysts for NRR as well as other catalytic applications.
