Effects of Size and Microstructures on Infrared Spectra of Pyrolusites

Abstract

Nanofibrous pyrolusite (β-MnO2) was synthesized. The particle shape changes from nanofibers to nanoparticles after grinding, and the phase structure does not change. The local environment around the central manganese ion has a slight change in nanoparticles related to nanofibers. Fourier transform infrared (FTIR) spectra showed that A2u mode frequency shifts from 514 cm−1 to 574 cm−1 to 617 cm−1 gradually while the particle shape and size change from long nanofibers to short fibers and to nanoparticles. The extra vibrational band that is unpredicted by factor group analysis originates from the contribution of A2u mode of the particles with different sizes and shapes in the studied sample. On the basis of Rietveld refinement analysis of XRD profiles and the FTIR spectra, we think that two kinds of MnO6 octahedral geometries, i.e., 4 long+2 short and 4 short+2 long, could exist in pyrolusites synthesized by different route. The maximum vibrational frequency in the FTIR spectra of pyrolusites is sensitive to these micro-structures. Assignment of four vibrational bands in the middle and far infrared region has been made.