A galvanic replacement reaction and the Kirkendall effect in the room-temperature synthesis of tubular NiSe2: a nanozyme catalyst with peroxidase-like activity. Issue 34 (10th August 2022)

• Record Type: Journal Article
• Authors: Sarkar, Sougata; Negishi, Yuichi; Pal, Tarasankar
• Is Part Of: Dalton transactions. Volume 51:Issue 34(2022)
• Page Start: 12904
• Page End: 12914
• Publication Date: 2022-08-10
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt01787c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A GRR and the Kirkendall effect assist the evolution of NiSe2 tubular nanostructures at room temperature from a Ni nanowire template, and these show peroxidase nanozyme activity. Abstract : 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 Ni 2+ /Ni and SeO3 2− /Se redox couples. Moreover, the selenium nanoparticles over the NiNW surface and the oxidized Ni 2+ 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.