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引用次数: 0
摘要
单原子纳米酶(SAzymes)是一种极具发展前景的新一代纳米酶。然而,它们的广泛应用仍然受到低反应活性的严重限制,这主要是由于低效的场地利用和缓慢的反应动力学。在此,我们提供了一种新的方法,通过化学气相沉积在高弯曲表面上最大化可访问的Fe - N - C位点。与具有平面Fe - N4位点的传统单铁原子催化剂(FeSA)相比,该创新催化剂表现出优越的多酶样活性。具体而言,对于过氧化物酶样活性,hFeSA的最大反应速度为1.91×10‐7 M s‐1,催化常数为5.78 s‐1,比活性为177.5 U/mg,分别比传统FeSA高9.67倍、2.56倍和9.56倍。同样,对于类似氧化酶的活性,hFeSA的最大反应速度为2.84×10‐7 M s‐1,催化常数为4.3 s‐1,比活性为76.27 U/mg,分别比FeSA提高了11.18倍、2.97倍和12.01倍。这些结果强调了hFeSA在显著提高多酶样活性方面的显著优势。此外,理论计算表明,固定在弯曲表面上的单个铁原子可以有效地降低能垒,从而提高Fe - N4位点的固有活性,加速反应动力学。
Maximizing Accessible Fe‐N‐C Sites on Highly Curved Surfaces via Chemical Vapor Deposition for Boosting Multienzyme‐like Activities of Single‐Atom Nanozymes
Single‐atom nanozymes (SAzymes) have emerged as a highly promising class of next‐generation nanozymes. However, their widespread application remains significantly restricted by low reaction activity, primarily attributed to inefficient site utilization and sluggish reaction kinetics. Herein, we provided a novel approach to maximize accessible Fe‐N‐C sites on a highly curved surface through chemical vapor deposition. This innovative catalyst demonstrated superior multienzyme‐like activities compared to the conventional single iron atom catalyst (FeSA) with planar Fe‐N4 sites. Specifically, for peroxidase‐like activity, the hFeSA exhibited a maximal reaction velocity of 1.91×10‐7 M s‐1, a catalytic constant of 5.78 s‐1, and a specific activity of 177.5 U/mg, which were 9.67‐fold, 2.56‐fold, and 9.56‐fold higher than those of the conventional FeSA, respectively. Similarly, for oxidase‐like activity, the hFeSA achieved a maximal reaction velocity of 2.84×10‐7 M s‐1, a catalytic constant of 4.3 s‐1, and a specific activity of 76.27 U/mg, representing enhancements of 11.18‐fold, 2.97‐fold, and 12.01‐fold over FeSA, respectively. These results underscore the significant advantages of hFeSA in dramatically enhancing multienzyme‐like activities. Furthermore, theoretical calculations revealed that single iron atoms anchored on curved surfaces can effectively lower the energy barrier, thereby enhancing the intrinsic activity of the Fe‐N4 sites and accelerating reaction kinetics.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.