Issue 23, 2024

The dehydration mechanism of Na and K birnessites: a comprehensive multitechnique study

Abstract

The structural, spectroscopic and electronic properties of Na and K birnessites were investigated from ambient conditions (birA) to complete dehydration, and the involved mechanisms were scrutinized. Density Functional Theory (DFT) simulations were employed to derive structural models for lamellar A0.33MnO2·xH2O (A = Na+ or K+, x = 0 or 0.66), subsequently compared with the experimental results obtained for Na0.30MnO2·0.75H2O and K0.22MnO2·0.77H2O materials. Thermal analysis (TGA-DSC), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, and Near Ambient Pressure X-ray Photoemission Spectroscopy (NAP-XPS) measurements were conducted for both birnessites. Dehydration under vacuum, annealing, or controlled relative humidity were considered. Results indicated that complete birnessite dehydration was a two-stage process. In the first stage, water removal from the interlayer of fully hydrated birnessite (birA) down to a molar H2O/A ratio of ∼2 (birB) led to the progressive shrinkage of the interlayer distance (3% for Na birnessite, 1% for K birnessite). In the second stage, water-free (birC) domains with a shorter interlayer distance (20% for Na birnessite, 10% for K birnessite) appeared and coexisted with birB domains. Then, birB was essentially transformed into birC when complete dehydration was achieved. The vibrational properties of birA were consistent with strong intermolecular interactions among water molecules, whereas partially dehydrated birnessite (birB) showed a distinct feature, with 3 (for Na-bir) and 2 (for K-bir) vibrations that were reproduced by DFT calculations for organized water into the interlayer (x = 0.66). The study also demonstrated that the electronic structure of Na birnessite depends on the interlayer water content. The external Na+ electronic level (Na 2p) was slightly destabilized (+0.3 eV binding energy) under near ambient conditions (birA) compared to drier conditions (birB and birC).

Graphical abstract: The dehydration mechanism of Na and K birnessites: a comprehensive multitechnique study

Supplementary files

Article information

Article type
Paper
Submitted
28 Feb 2024
Accepted
03 May 2024
First published
10 May 2024
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2024,53, 9952-9963

The dehydration mechanism of Na and K birnessites: a comprehensive multitechnique study

E. André, D. Cornu, L. Pérez Ramírez, P. Durand, J.-J. Gallet, F. Bournel, F. Rochet, C. Ruby, C. Carteret and R. Coustel, Dalton Trans., 2024, 53, 9952 DOI: 10.1039/D4DT00588K

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