Abstract Nanomaterials with enzyme-like activities, i.e., nanozymes, have aroused wide concern in biocatalysis. Fe-N-C single-atom catalysts with atomically dispersed FeNx as active sites, defined as Fe-N-C single-atom nanozymes, have the structure similar to some heme enzymes and therefore can mimic the enzyme-like activities. However, they are still subject to the limited biocatalytic activity and selectivity because of the grand challenge in rationally tuning the electronic structure of central Fe atoms and achieving their superior performances approaching nature heme enzymes. Herein, we demonstrate that boron-doped Fe-N-C single-atom nanozymes with an intrinsic charge transfer can work much better and achieve the significantly enhanced peroxidase-like activities and selectivities. Theoretical calculations reveal that boron-induced charge transfer effects can be capable of modulating the positive charge of the central Fe atom to reduce the energy barrier of the formation of hydroxyl radical and therefore boost the peroxidase-like activity. The boron-doped Fe-N-C single-atom nanozymes can achieve vivid mimicking nature peroxidase and finally show their promising applications in the detection of enzyme activity and small molecule. This work opens a new route in the rational synthesis of more advanced nanozymes at the atomic scale and bridges the gap between nanozymes and natural enzymes.

中文翻译：

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硼掺杂的 Fe-NC 单原子纳米酶特异性地增强过氧化物酶样活性

摘要 具有类酶活性的纳米材料，即纳米酶，在生物催化领域引起了广泛关注。以原子分散的FeNx为活性位点的Fe-NC单原子催化剂，定义为Fe-NC单原子纳米酶，其结构类似于一些血红素酶，因此可以模拟类酶活性。然而，由于在合理调整中心铁原子的电子结构和实现其接近天然血红素酶的优异性能方面面临巨大挑战，它们仍然受到有限的生物催化活性和选择性的影响。在此，我们证明具有固有电荷转移的硼掺杂 Fe-NC 单原子纳米酶可以更好地工作，并实现显着增强的类过氧化物酶活性和选择性。理论计算表明，硼诱导的电荷转移效应能够调节中心铁原子的正电荷，从而降低形成羟基自由基的能垒，从而提高类过氧化物酶的活性。硼掺杂的Fe-NC单原子纳米酶可以生动地模仿自然过氧化物酶，最终在酶活性和小分子检测中显示出其广阔的应用前景。这项工作为在原子尺度上合理合成更先进的纳米酶开辟了一条新途径，并弥合了纳米酶与天然酶之间的差距。硼掺杂的Fe-NC单原子纳米酶可以生动地模仿自然过氧化物酶，最终在酶活性和小分子检测中显示出其广阔的应用前景。这项工作为在原子尺度上合理合成更先进的纳米酶开辟了一条新途径，并弥合了纳米酶与天然酶之间的差距。硼掺杂的Fe-NC单原子纳米酶可以生动地模仿自然过氧化物酶，最终在酶活性和小分子检测中显示出其广阔的应用前景。这项工作为在原子尺度上合理合成更先进的纳米酶开辟了一条新途径，并弥合了纳米酶与天然酶之间的差距。