The influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties.
In this work, a new approach to construct self‐assembled hybrid systems based on natural PSII‐enriched thylakoid membranes (PSII BBY) is demonstrated. Superfine m‐WO3 NPs (≈1–2 nm) are introduced into PSII BBY. Transmission electron microscopy (TEM) measurements showed that even the highest concentrations of NPs used did not degrade the PSII BBY membranes. Using atomic force microscopy (AFM), it is shown that the organization of PSII BBY depends strongly on the concentration of NPs applied. This proved that the superfine NPs can easily penetrate the thylakoid membrane and interact with its components. These changes are also related to the modified energy transfer between the external light‐harvesting antennas and the PSII reaction center, shown by absorption and fluorescence experiments. The biohybrid system shows stability at pH 6.5, the native operating environment of PSII, so a high rate of O2 evolution is expected. In addition, the light‐induced water‐splitting process can be further stimulated by the direct interaction of superfine WO3 NPs with the donor and acceptor sides of PSII. The water‐splitting activity and stability of this colloidal system are under investigation.Research Highlights The phenomenon of the self‐organization of a biohybrid system composed of thylakoid membranes enriched in photosystem II and superfine WO3 nanoparticles is studied using AFM and TEM. A strong dependence of the organization of PSII complexes within PSII BBY membranes on the concentration of NPs applied is observed. This observation turns out to be crucial to understand the complexity of the mechanism of the action of WO3 NPs on modifications of energy transfer from external antenna complexes to the PSII reaction center.
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