STUDIES OF 2D LAYERED MnO2 AND MoS2 FOR ANTIBACTERIAL AND ELECTROCHEMICAL APPLICATIONS

Abstract

The goal of the dissertation was to optimize synthetic parameters to tune the properties of two layered materials, MoS2 and MnO2 for applications such as antibacterial, energy storage and water remediation. Two aspects of the materials were investigated. Firstly, the synthetic parameters were tuned to prepare material with different morphologies and then the effect of morphology and structure on interaction with bacterial cells was studied. In the second part, the research was focused on tuning the synthetic parameters to improve the intrinsic conductivity of the material for electrocatalytic applications. This dissertation work primarily focuses on understanding the catalytic and antibacterial activity of layered MnO2 and MoS2. One research effort was focused on the antibacterial mode of action of layered nanosheets of MnO2 and MoS2 toward Gram-positive and Gram-negative bacteria. Bacillus subtilis and Escherichia coli bacteria were chosen as model organisms, which were treated individually with randomly oriented and vertically aligned nanosheets. Viability measurements of bacteria, by flow cytometry and fluorescence imaging, showed that vertically aligned MnO2 and MoS2 nanosheets revealed the highest antimicrobial activity and that Gram-positive bacteria showed a higher loss in membrane integrity, compared to Gram-negative bacteria. Moreover, scanning electron microscopy images suggested that the nanosheets compromised the cell wall upon interaction, which led to significant bacterial morphological changes. We propose that the peptidoglycan mesh in the bacterial wall is likely the primary target of the 2D layered nanomaterials. Another focus of the dissertation research investigated the effect of structural and geometrical changes of layered materials on the properties which affect the intrinsic conductivity of material. In the first study, the electrocatalytic activity of layer-by-layer (LbL) deposited 1T'-MoS2 (metallic phase) on a fluorine-doped tin oxide (FTO) substrate was investigated for the hydrogen evolution reaction (HER) as a function of layer number. Conversion of the deposited 1T'-MoS2 to the semiconducting 2H-MoS2 phase via exposure to 532 nm wavelength light, confirmed by Raman spectroscopy and scanning tunneling spectroscopy (STS), allowed a direct comparison of the HER activity of the two phases at a constant mass loading and surface area on the same substrate. The morphology, thickness and roughness of the deposited MoS2 layers as a function of the number of deposition cycles were investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The results showed that the average roughness of the surface increased with the number of deposition cycles, indicating that the thickness of the deposited layered material became heterogeneous with increasing cycle number. For a given number of deposition cycles (i.e., similar mass loading), 1T'-MoS2 exhibited a lower overpotential for the HER than the 2H-MoS2 phase. For example, at a sample thickness of 19.7 ± 2.8 nm (20 LbL cycle) the overpotentials for the HER for 1T'-MoS2 and 2H-MoS2 were 0.54 and 0.61 V, respectively (at a current density of -2 mA/cm2). Overall, the overpotential for HER associated with both MoS2 phases decreased as the mass loading increased. Our study revealed the heterogenous formation of few layer 1T'-MoS2 on the surface, providing a novel approach to improve HER activity towards water splitting applications. A further research effort studied birnessite, focusing on the activity of exfoliated birnessite and the role of birnessite defects for water oxidation. The catalytic activity of layered MnO2 has been studied widely. Birnessite has the lowest oxygen evolution reaction (OER) activity in alkaline media compared to other manganese oxide phases. A motivation for the study was to investigate the OER activity of exfoliated-restacked birnessite sheets which can lead to a better understanding of the birnessite catalytic performance. Synthesized birnessite was exfoliated into monolayer sheets via a cation exchange method. Characterization of the birnessite monolayer sheets using AFM and scanning tunneling microscopy (STM) revealed the presence of the holes and point defects. The phase and conductivity of monolayer sheets were measured by STS. Electrochemical characterizations of exfoliated birnessite have shown that nanosheets of birnessite expose a great number of active sites and exhibit facile electrode kinetics as a result of the defective sheets. In particular, the overpotential of exfoliated birnessite synthesized at 400°C was 450 mV compared to 550 mV for the exfoliated birnessite synthesized at 1000°C. The results indicate that the defective exfoliated sheets have higher conductivity and higher OER activity compared to defect free exfoliated sheets. Additional research of birnessite focused on its activity for the arsenite (i.e., As(III)) oxidation reaction. Birnessite polytypes were synthesized by decomposition of KMnO4 at different temperatures, and three polytypes including two-layer orthogonal (2O), two-layer hexagonal (2H) and three-layer rhombohedral (3R) were identified in the samples. The synthetic temperature controlled the phase formation and heterogeneity of the phases. Birnessite synthesized at 600°C contained 2H/3R phases which showed the highest activity with first order rate constant of the 0.741 h-1 which is 3.6 and 24 times higher than Birnessite synthesized at 800 and 1000°C, respectively. The structural change of the polytype birnessite after As(III) oxidation was studied by pair distribution function experiment. Results indicated that Mn4+ in the birnessite was reduced to Mn3+ and that this reduced species migrated from the in-layer position to the interlayer region. Furthermore, we report the results of in-situ AFM of birnessite sheets exposed to arsenite which provides a detailed understanding of the arsenite oxidation reaction at the birnessite surface. The reductive dissolution of birnessite was shown to be more active on the edges compared to the basal plane of birnessite. Our findings have important implications for material design aimed at removal of arsenite in purification processes.