Unraveling the Effect of the Chemical and Structural Composition of ZnxNi1−xFe2O4 on the Electron Transfer at the Electrochemical Interface

Author:

Madagalam Mallikarjun123ORCID,Bartoli Mattia34,Rosito Michele1,Blangetti Nicola1,Etzi Coller Pascuzzi Marco4,Padovano Elisa13,Bonelli Barbara13,Carrara Sandro2,Tagliaferro Alberto13

Affiliation:

1. Department of Applied Science and Technology Politecnico di Torino Duca degli Abruzzi 24 10129 Torino Italy

2. Bio/CMOS Interfaces Laboratory École Polytechnique Fédérale de Lausanne Rue de la Maladière 71b 2000 Neuchâtel Switzerland

3. National Interuniversity Consortium of Materials Science and Technology Unit of Torino – Politecnico di Torino Via Giuseppe Giusti, 9 50121 Florence Italy

4. Center for Sustainable Future Technologies Fondazione Istituto Italiano di Tecnologia Via Livorno 60 10144 Torino Italy

Abstract

In order to deepen the understanding of the role of transition metal oxides in electron transfer at the electrochemical interface, the performance of Zn x Ni1−x Fe2O4 (x = 0, 0.2, 0.4, 0.6, 0.8, 1) nanomaterials in electrochemical sensing is studied. Nanomaterials are synthesized by simple autocombustion synthesis procedure. Field‐emission scanning electron microscopy characterization shows that the particles have a size between 30 and 70 nm with an average crystallite size between 24 and 35 nm. The bandgap energies of the nanomaterials, as estimated by UV–vis experiments, are in the 2.32–2.56 eV range. The valence band maximum is evaluated using X‐ray photoelectron spectroscopy and the position of the conduction band minimum is estimated. The ZnFe2O4 sensor has the best performances: highest rate constant (13.1 ± 2.8 ms−1), lowest peak‐to‐peak separation (386 ± 2 mV), and highest sensitivity (37.75 ± 0.17 μA mM−1). Its limit of detection (7.94 ± 0.04 μM) is second best, and its sensitivity is more than twice the sensitivity of the bare sensor (16.7 ± 0.9 μA mM−1). Nanomaterials energy bands mapping with the experimental redox potentials is performed to predict the electron transfer at the electrochemical interface, and the importance of surface states/defects is highlighted in the electron transfer mechanism.

Publisher

Wiley

Subject

General Earth and Planetary Sciences,General Environmental Science

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