Probing the Structure and Binding Mode of EDTA on the Surface of Mn₃O₄ Nanoparticles for Water Oxidation by Advanced Electron Paramagnetic Resonance Spectroscopy

Abstract

Identification of the surface structure of nanoparticles is important for understanding the catalytic mechanism and improving the properties of the particles. Here, we provide a detailed description of the coordination modes of ethylenediaminetetraacetate (EDTA) on Mn 3 O 4 nanoparticles at the atomic level, as obtained by advanced electron paramagnetic resonance (EPR) spectroscopy. Binding of EDTA to Mn 3 O 4 leads to dramatic changes in the EPR spectrum, with a 5-fold increase in the axial zero-field splitting parameter of Mn(II). This indicates significant changes in the coordination environment of the Mn(II) site; hence, the binding of EDTA causes a profound change in the electronic structure of the manganese site. Furthermore, the electron spin echo envelope modulation results reveal that two 14 N atoms of EDTA are directly coordinated to the Mn site and a water molecule is coordinated to the surface of the nanoparticles. An Fourier transform infrared spectroscopy study shows that the Ca(II) ion is coordinated to the carboxylic ligands via the pseudobridging mode. The EPR spectroscopic results provide an atomic picture of surface-modified Mn 3 O 4 nanoparticles for the first time. These results can enhance our understanding of the rational design of catalysts, for example, for the water oxidation reaction.

Surface Structures of Mn3O4 and the Partition of Oxidation States of Mn

“…Hausmannite (Mn 3 O 4 ) crystallizes in a tetragonal spinel-like structure ( I 4 1 / amd space group) below 1170 °C because of the Jahn–Teller effect . It has attracted great interest for its potential technological applications in electrocatalysis and water treatment. − It is hypothesized that the Mn­(III) instead of Mn­(II) or Mn­(IV) at the surface are more active catalytically . However, the surface structures are still to be revealed …”

Zinc tungstate encapsulated into a scarce Zn(ii)–viologen framework with photochromic, electrochromic and chemochromic properties

“…S7 †). 51 IR analysis and PXRD showed that there was no significant change after illumination (Fig. S8 †), which ruled out the possibility of photoisomerization and photodecomposition.…”