College of Engineering and Applied Sciences, Nanjing National Laboratory of Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, Nanjing University, Nanjing, Jiangsu, 210093, China.
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China.
Nat Commun. 2019 Feb 11;10(1):704. doi: 10.1038/s41467-019-08657-5.
A peroxidase catalyzes the oxidation of a substrate with a peroxide. The search for peroxidase-like and other enzyme-like nanomaterials (called nanozymes) mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. To fill this gap, here we investigate the occupancy of e orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide (including perovskite oxide) nanozymes. Both experimental measurements and density functional theory calculations reveal a volcano relationship between the e occupancy and nanozymes' activity, with the highest peroxidase-like activities corresponding to e occupancies of ~1.2. LaNiO, optimized based on the e occupancy, exhibits an activity one to two orders of magnitude higher than that of other representative peroxidase-like nanozymes. This study shows that the e occupancy is a predictive descriptor to guide the design of peroxidase-like nanozymes; in addition, it provides detailed insight into the catalytic mechanism of peroxidase-like nanozymes.
过氧化物酶催化过氧化物氧化底物。由于缺乏预测性描述符，过氧化物酶样和其他酶样纳米材料（称为纳米酶）的寻找主要依赖于反复试验的策略。为了填补这一空白，我们在这里研究了 e 轨道的占据情况，作为过渡金属氧化物（包括钙钛矿氧化物）纳米酶过氧化物酶样活性的可能描述符。实验测量和密度泛函理论计算都揭示了 e 占据与纳米酶活性之间的火山关系，e 占据约为 1.2 时对应着最高的过氧化物酶样活性。基于 e 占据优化的 LaNiO 表现出比其他代表性过氧化物酶样纳米酶高一个或两个数量级的活性。这项研究表明，e 占据是一种预测性描述符，可以指导过氧化物酶样纳米酶的设计；此外，它还提供了对过氧化物酶样纳米酶催化机制的详细见解。
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