Galvanic Replacement Reaction and Kirkendall Effect in Room Temperature Synthesis of Tubular NiSe2: A Nanozyme Catalyst with Peroxidase-Like Activity
Galvanic Replacement Reaction and Kirkendall Effect in Room Temperature Synthesis of Tubular NiSe2: A Nanozyme Catalyst with Peroxidase-Like Activity
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室温合成管状 NiSe2 中的电取代反应和柯肯德尔效应：具有类过氧化物酶活性的纳米酶催化剂
DOI：
10.1039/d2dt01787c
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
T. Pal
中科院分区：
文献类型：
--
作者：
S. Sarkar;Y. Negishi;T. Pal
在环境条件下合成硒化镍纳米结构仍然迷人，美观，节能，因为大多数报道的方法涉及高温技术。在这项工作中，我们报告了湿化学合成NiSe 2纳米结构在室温下。该方法以镍纳米线（NiNW）和亚硒酸作为活性成分开始。在亚硒酸中孵育NiNW后，零价金属镍逐渐氧化，纳米硒，还原产物，在原始NiNW表面上连续沉积。这种电化学控制的电流置换反应（GRR）有利地受Ni 2 +/Ni和SeO 32 −/Se氧化还原对的还原电位值控制。此外，在NiNW表面上的硒纳米颗粒和下面的氧化的Ni 2+然后在向内和向外扩散期间相互作用。元素/离子的不同扩散率导致空隙内部的产生，从而导致管状纳米结构。因此，GRR和纳米级Kirkendall效应共同保持接合，导致形成中空的NiSe 2纳米管结构。然后，我们巧妙地利用这种异质硫族化物纳米结构材料作为过氧化物酶模拟物的人工酶。这提供了一种肉眼检测溶液中过氧化物的方法。谷胱甘肽的存在下，过氧化物酶的活性被选择性地抑制。因此，同时开发了用于选择性检测该生物硫醇的比色测定法。底物的固有纳米酶活性是迄今为止未知的，因此可以用其他纳米结构的硒化镍材料进一步探索。
The synthesis of nickel selenide nanostructures under ambient conditions remains fascinating, aesthetically beautiful, and energy efficient, as most reported methods involve high-temperature techniques. In this work, we have reported the wet chemical synthesis of NiSe2 nanostructures at room temperature. The approach starts with nickel nanowires (NiNW) and selenous acid as active ingredients. Upon the incubation of NiNW in selenous acid, zero-valent metallic nickel gradually oxidised with the successive deposition of nano-selenium, a reductive product, over the pristine NiNW surface. This thermodynamically controlled galvanic replacement reaction (GRR) is favourably governed by the reduction potential values of the Ni2+/Ni and SeO32−/Se redox couples. Moreover, the selenium nanoparticles over the NiNW surface and the oxidized Ni2+ underneath then interplay during inward and outward diffusion. The different diffusivities of the elements/ions cause the generation of void interiors, thus resulting in tubular nanostructures. Therefore, both the GRR and nanoscale Kirkendall effect jointly remain engaged, resulting in the formation of hollow NiSe2 nanotubular structures. Then, we ably exploit this heterogeneous chalcogenide nanostructure material as an artificial enzyme for peroxidase mimics. This provides a method for the naked-eye detection of peroxide in solution. The peroxidase activity was selectively restrained in the presence of glutathione. Hence, a colourimetric assay was simultaneously developed for the selective detection of this biothiol. The intrinsic nanozyme activity of the substrate is hitherto unknown and can, hence, be explored further with other nanostructured nickel selenide materials.