Yan Tingyu, Wang Siyao, Lang Simone, Wang Zhongxu, Lin Shiru, Zhao Jingxiang
Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, China.
Division of Chemistry and Biochemistry, Texas Woman's University, Denton, TX 76204, USA.
J Colloid Interface Sci. 2025 Apr;683(Pt 2):1067-1076. doi: 10.1016/j.jcis.2024.12.243. Epub 2025 Jan 2.
Electrocatalytic NO reduction (NORR) to NH represents a promising approach for converting hazardous NO waste gases into high-value NH products under ambient conditions. However, exploring stable, low-cost, and highly efficient catalysts to enhance the NO-to-NH conversion process remains a significant challenge. Herein, through systematic computational studies based on density functional theory (DFT), we rationally designed transition metal triatomic cluster supported on graphdiyne (TM/GDY) as potential single-cluster catalysts for high-performance NORR. The results indicated that the GDY support is incredibly effective at immobilizing these triatomic metal clusters, preventing metal aggregation and dissolution. Furthermore, the TM/GDY systems exhibit tunable reactivity for NO activation due to the synergistic effect of triple-metal sites. Among all examined candidates, Ni/GDY demonstrates the highest NORR catalytic performance with a record low limiting potential of -0.05 V. Notably, NO adsorption strength was identified as an effective descriptor to rationalize the NORR activity trend, which is highly dependent on the amount of the carrying charges on the anchored TM clusters. Additionally, the hydrogenation steps during NORR are kinetically feasible on Ni/GDY with a small kinetic barrier of 0.34 V for the rate-determining step, corresponding to an outstanding turnover frequency (3.03 × 10) s per site at 300 K for NH generation, implying an ultra-fast reaction rate. Our work not only identified promising NORR catalysts but also provided valuable insights for rationally designing atomically precise novel catalysts for the resource utilization of small molecules.
电催化将一氧化氮还原为氨是一种在环境条件下将有害的一氧化氮废气转化为高价值氨产品的有前景的方法。然而，探索稳定、低成本且高效的催化剂以增强一氧化氮到氨的转化过程仍然是一项重大挑战。在此，通过基于密度泛函理论（DFT）的系统计算研究，我们合理设计了负载在石墨炔上的过渡金属三原子簇（TM/GDY）作为高性能一氧化氮还原反应的潜在单簇催化剂。结果表明，石墨炔载体在固定这些三原子金属簇方面非常有效，可防止金属聚集和溶解。此外，由于三金属位点的协同效应，TM/GDY体系对一氧化氮活化表现出可调的反应活性。在所有研究的候选物中，Ni/GDY表现出最高的一氧化氮还原反应催化性能，其极限电位低至 -0.05 V，创历史记录。值得注意的是，一氧化氮吸附强度被确定为合理化一氧化氮还原反应活性趋势的有效描述符，这高度依赖于锚定的TM簇上的携带电荷量。此外，一氧化氮还原反应过程中的氢化步骤在Ni/GDY上在动力学上是可行的，速率决定步骤具有0.34 V的小动力学势垒，对应于在300 K下氨生成时每个位点出色的周转频率（3.03×10）s，这意味着超快的反应速率。我们的工作不仅确定了有前景的一氧化氮还原反应催化剂，还为合理设计用于小分子资源利用的原子精确新型催化剂提供了有价值的见解。
