Hydrolase-mimicking nanozymes have received increasing attention in recent years, but the effective rational design and development of these materials has not been realized, as they are not at present considered a critical research target. Herein, we report that Zn-doped mesoporous ceria (Zn-m-ceria) engineered to have an abundance of two different active sites with different functions—one that allows both co-adsorption binding of organophosphate (OP) and water and another that serves as a general base—has significant organophosphorus hydrolase (OPH)-like catalytic activity. Specifically, Zn-m-ceria exhibits a catalytic efficiency over 75- and 25-fold higher than those of m-ceria and natural OPH, respectively. First-principles calculations reveal the importance of Zn for the OPH-mimicking activity of the material, promoting substrate adsorption and proton-binding. The OPH-like Zn-m-ceria catalyst is successfully applied to detect a model OP, methyl paraoxon, in spiked tap water samples with excellent sensitivity, stability, and detection precision. We expect that these findings will promote research based on the rational engineering of the active site of nanozymes and efficient strategies for obtaining a diverse range of catalysts that mimic natural enzymes, and hence the utilization in real-world applications of enzyme-mimicking catalysts with properties superior to their natural analogs should follow.

近年来，模拟水解酶的纳米酶受到越来越多的关注，但这些材料的有效合理设计和开发尚未实现，因为它们目前不被认为是关键的研究目标。在此，我们报道了掺锌介孔二氧化铈（Zn-m-二氧化铈）经过改造，具有丰富的两个具有不同功能的不同活性位点——一个允许有机磷酸盐（OP）和水的共吸附结合，另一个则可以发挥作用。作为通用碱——具有显着的有机磷水解酶 (OPH) 样催化活性。具体而言，Zn-m-二氧化铈的催化效率分别比 m-二氧化铈和天然 OPH 高 75 倍和 25 倍。第一性原理计算揭示了 Zn 对于材料的 OPH 模拟活性、促进底物吸附和质子结合的重要性。类OPH Zn-m-二氧化铈催化剂已成功应用于检测加标自来水样品中的OP（甲基对氧磷）模型，具有出色的灵敏度、稳定性和检测精度。我们期望这些发现将促进基于纳米酶活性位点的合理工程的研究以及获得各种模拟天然酶的催化剂的有效策略，从而促进具有特性的模拟酶催化剂在现实世界中的应用优于其天然类似物的结果应该随之而来。