Effect of Phosphorus Modulation in Iron Single‐Atom Catalysts for Peroxidase Mimicking
Effect of Phosphorus Modulation in Iron Single‐Atom Catalysts for Peroxidase Mimicking
复制标题
铁单原子催化剂中磷调节对模拟过氧化物酶的影响
DOI：
10.1002/adma.202209633
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发表时间：
2023
影响因子：
29.4
通讯作者：
Beckman, Scott P.
中科院分区：
文献类型：
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作者：
Ding, Shichao;Barr, Jordan Alysia;Lyu, Zhaoyuan;Zhang, Fangyu;Wang, Maoyu;Tieu, Peter;Li, Xin;Engelhard, Mark H.;Feng, Zhenxing;Beckman, Scott P.
Fe-N-C单原子催化剂(SACs)由于其在碳载体上有明确的孤立铁活性中心，有效地模拟了天然过氧化物酶活性中心的结构，表现出优异的类过氧化物酶(POD)催化活性。为了进一步满足多样化的生物传感应用的要求，SAC POD样活性仍需不断增强。在这里，引入磷(P)杂原子来增强Fe-N-C囊的POD样活性。设计并合成了富含Fe-N4活性中心的一维碳纳米线(FeNCP/NW)催化剂，将P原子掺杂到碳基质中，通过长程相互作用影响Fe中心。实验结果表明，与未掺杂工艺相比，磷掺杂工艺能更好地提高POD的类POD活性，具有良好的选择性和稳定性。机理分析结果表明，在SAC中引入P可以显著增强POD样活性，但随着P含量的增加，这种作用变得不明显。作为概念的证明，FeNCP/NW被用于酶的级联平台，用于神经递质乙酰胆碱的高灵敏比色检测。
Fe–N–C single‐atom catalysts (SACs) exhibit excellent peroxidase (POD)‐like catalytic activity, owing to their well‐defined isolated iron active sites on the carbon substrate, which effectively mimic the structure of natural peroxidase's active center. To further meet the requirements of diverse biosensing applications, SAC POD‐like activity still needs to be continuously enhanced. Herein, a phosphorus (P) heteroatom is introduced to boost the POD‐like activity of Fe–N–C SACs. A 1D carbon nanowire (FeNCP/NW) catalyst with enriched Fe–N4active sites is designed and synthesized, and P atoms are doped in the carbon matrix to affect the Fe center through long‐range interaction. The experimental results show that the P‐doping process can boost the POD‐like activity more than the non‐P‐doped one, with excellent selectivity and stability. The mechanism analysis results show that the introduction of P into SAC can greatly enhance POD‐like activity initially, but its effect becomes insignificant with increasing amount of P. As a proof of concept, FeNCP/NW is employed in an enzyme cascade platform for highly sensitive colorimetric detection of the neurotransmitter acetylcholine.