School of Mechanical and Material Engineering, Washington State University, Pullman, WA, 99164, USA.
Department of NanoEngineering and Chemical Engineering Program, University of California, San Diego, La Jolla, CA, 92093, USA.
Adv Mater. 2024 Mar;36(10):e2209633. doi: 10.1002/adma.202209633. Epub 2023 Mar 13.
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-N active 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.
铁-氮-碳单原子催化剂（SACs）因其在碳基底上具有明确的孤立铁活性位，有效地模拟了天然过氧化物酶活性中心的结构，从而表现出优异的过氧化物酶（POD）样催化活性。为了进一步满足各种生物传感应用的要求，SAC POD 样活性仍需要不断增强。在此，引入磷（P）杂原子来提高 Fe-N-C SAC 的 POD 样活性。设计并合成了具有丰富的 Fe-N 活性位的一维碳纳米线（FeNCP/NW）催化剂，并通过远程相互作用将 P 原子掺杂到碳基质中以影响 Fe 中心。实验结果表明，P 掺杂过程可以提高 POD 样活性，比未掺杂 P 的活性更高，具有优异的选择性和稳定性。机理分析结果表明，最初将 P 引入 SAC 中可以极大地提高 POD 样活性，但随着 P 含量的增加，其效果变得不明显。作为概念验证，FeNCP/NW 被用于酶级联平台，用于对神经递质乙酰胆碱进行高灵敏度比色检测。
