Depletable peroxidase-like activity of Fe(3)O(4) nanozymes accompanied with separate migration of electrons and iron ions.
Depletable peroxidase-like activity of Fe(3)O(4) nanozymes accompanied with separate migration of electrons and iron ions.
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DOI：
10.1038/s41467-022-33098-y
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发表时间：
2022-09-12
影响因子：
16.6
通讯作者：
Zhang, Yu
中科院分区：
文献类型：
--
作者：
Dong, Haijiao;Du, Wei;Dong, Jian;Che, Renchao;Kong, Fei;Cheng, Wenlong;Ma, Ming;Gu, Ning;Zhang, Yu
作为开创性的Fe3O4纳米酶，其明确的过氧化物酶（POD）样催化机制仍然难以捉摸。虽然许多研究已经提出了表面Fe 2+诱导的Fenton反应占其POD样活性，很少有集中在内部原子的变化和它们的贡献的催化反应。在这里，我们报告说，Fe3O4中的Fe 2+可以通过Fe 2 +-O-Fe 3+链将电子转移到表面，再生表面Fe 2+，并使持续的POD样催化反应成为可能。该过程通常伴随着过量氧化的Fe 3+从晶格向外迁移而发生，这是一个限速步骤。Fe3O4纳米酶在长时间催化后，会发生相转变，生成具有耗尽POD活性的γ-Fe2O3。具有参与电子转移和离子迁移的内部原子的纳米酶的这种自耗尽特性在磷酸铁锂纳米颗粒上得到了很好的验证。我们揭示了一个被忽视的问题，考虑表面和内部原子的必要性时，设计，调制和应用纳米酶。过氧化物酶样Fe3O4纳米酶的机制仍然是难以捉摸的。在这里，作者显示了Fe（II）离子的电子转移机制，以再生表面Fe（II）和相关的相变和活性耗尽。
As pioneering Fe3O4 nanozymes, their explicit peroxidase (POD)-like catalytic mechanism remains elusive. Although many studies have proposed surface Fe2+-induced Fenton-like reactions accounting for their POD-like activity, few have focused on the internal atomic changes and their contribution to the catalytic reaction. Here we report that Fe2+ within Fe3O4 can transfer electrons to the surface via the Fe2+-O-Fe3+ chain, regenerating the surface Fe2+ and enabling a sustained POD-like catalytic reaction. This process usually occurs with the outward migration of excess oxidized Fe3+ from the lattice, which is a rate-limiting step. After prolonged catalysis, Fe3O4 nanozymes suffer the phase transformation to γ-Fe2O3 with depletable POD-like activity. This self-depleting characteristic of nanozymes with internal atoms involved in electron transfer and ion migration is well validated on lithium iron phosphate nanoparticles. We reveal a neglected issue concerning the necessity of considering both surface and internal atoms when designing, modulating, and applying nanozymes. The mechanism of peroxidase-like Fe3O4 nanozymes remains elusive. Here, the authors show the electron transfer mechanism of Fe(II) ions to regenerate surface Fe(II) and the related phase transformation and depletion of activity.
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