A novel hierarchical nanotube array (NTA) with a massive layered top and discretely separated nanotubes in a core–shell structure, that is, nickel–cobalt metallic core and nickel–cobalt layered double hydroxide shell (NiCo@NiCo LDH), is grown on carbon fiber cloth (CFC) by template-assisted electrodeposition for high-performance supercapacitor application. The synthesized NiCo@NiCo LDH NTAs/CFC shows high capacitance of 2200 F g−1 at a current density of 5 A g−1, while 98.8% of its initial capacitance is retained after 5000 cycles. When the current density is increased from 1 to 20 A g−1, the capacitance loss is less than 20%, demonstrating excellent rate capability. A highly flexible all-solid-state battery-type supercapacitor is successfully fabricated with NiCo LDH NTAs/CFC as the positive electrode and electrospun carbon fibers/CFC as the negative electrode, showing a maximum specific capacitance of 319 F g−1, a high energy density of 100 W h kg−1 at 1.5 kW kg−1, and good cycling stability (98.6% after 3000 cycles). These fascinating electrochemical properties are resulted from the novel structure of electrode materials and synergistic contributions from the two electrodes, showing great potential for energy storage applications.

Design of Hierarchical NiCo@NiCo Layered Double Hydroxide Core–Shell Structured Nanotube Array for High-Performance Flexible All-Solid-State Battery-Type Supercapacitors

Cobalt doped ZnO nanodisks and nanorods were synthesized by a facile wet chemical method and well characterized by X-ray diffraction, field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy, photoluminescence spectroscopy, Raman spectroscopy and UV-visible absorption spectroscopy. The photocatalytic activities were evaluated for sunlight driven degradation of an aqueous methylene blue (MB) solution. The results showed that Co doped ZnO nanodisks and nanorods exhibit highly enhanced photocatalytic activity, as compared to pure ZnO nanodisks and nanorods. The enhanced photocatalytic activities of Co doped ZnO nanostructures were attributed to the combined effects of enhanced surface area of ZnO nanodisks and improved charge separation efficiency due to optimal Co doping which inhibit recombination of photogenerated charge carriers. The possible mechanism for the enhanced photocatalytic activity of Co doped ZnO nanostructures is tentatively proposed.

Enhanced photocatalytic activity of Co doped ZnO nanodisks and nanorods prepared by a facile wet chemical method

We report here enhancement of ferromagnetism in pure ZnO upon thermal annealing with the ferromagnetic transition temperature Tc above room temperature. We observe a finite coercive field upto 300K and a finite thermoremanent magnetization upto 340K for the annealed sample. We propose that magnetic moments can form at anionic vacancy clusters. Ferromagnetism can occur due to either superexchange between vacancy clusters via isolated F+ centers, or through a limited electron delocalization between vacancy clusters. Isolated vacancy clusters or isolated F+ centers give rise to a strong paramagnetic like behaviour below 10K.

Enhancement of ferromagnetism upon thermal annealing in pure ZnO

We report on the oxygen vacancy induced ferromagnetism (FM) at and above room temperature in undoped TiO2 nanoporous nanoribbons synthesized by a solvothermal route. The origin of FM in as-synthesized and vacuum annealed undoped nanoribbons grown for different reaction durations followed by calcinations was investigated by several experimental tools. X-Ray diffraction pattern and micro-Raman studies reveal the TiO2(B), TiO2(B)-anatase, and anatase–rutile mixed phases of TiO2 structure. Field emission scanning electron microscopy and transmission electron microscopy observations reveal nanoribbons with uniform pore distribution and nanopits/nanobricks formed on the surface. These samples exhibit strong visible photoluminescence associated with oxygen vacancies and a clear ferromagnetic hysteresis loop, both of which dramatically enhanced after vacuum annealing. Direct evidence of oxygen vacancies and related Ti3+ in the as-prepared and vacuum annealed TiO2 samples are provided through X-ray photoelectron spectroscopy analysis. Micro-Raman, infrared absorption and optical absorption spectroscopic analyses further support our conclusion. The observed room temperature FM in undoped TiO2 nanoribbons is quantitatively analyzed and explained through a model involving bound magnetic polarons (BMP), which include an electron locally trapped by an oxygen vacancy with the trapped electron occupying an orbital overlapping with the unpaired electron (3d1) of Ti3+ ion. Our analysis interestingly shows that the calculated BMP concentration scales linearly with concentration of oxygen vacancies and provides a stronger footing for exploiting defect engineered ferromagnetism in undoped TiO2 nanostructures. The development of such highly porous TiO2 nanoribbons constitutes an important step towards realizing improved visible light photocatalytic and photovoltaic applications of this novel material.

Evidence of oxygen vacancy induced room temperature ferromagnetism in solvothermally synthesized undoped TiO2 nanoribbons.

https://pure.mpg.de/pubman/item/item_3314161_3/component/file_3324933/1-s2.0-S0370157320303525-main.pdf

Beyond skyrmions: Review and perspectives of alternative magnetic quasiparticles

We report on the occurrence of high temperature ferromagnetism (FM) in ZnO nanoparticles (NPs) doped with Co-atoms. ZnO NPs of two different initial sizes are doped with 3% and 5% Co using ball milling and FM is studied at room temperature and above. X-ray diffraction and high-resolution transmission electron microscopy analysis confirm the absence of metallic Co clusters or any other phase different from wurtzite-type ZnO. UV-visible absorption studies show change in band structure and photoluminescence studies show green emission band at 520 nm indicating incorporation of Co-atoms and presence of oxygen vacancy defects, respectively in ZnO lattice. Micro-Raman studies of doped samples shows defect related additional bands at 547 and 574 cm−1. XRD and Raman spectra provide clear evidence for strain in the doped ZnO NPs. The field dependence of magnetization (M-H curve) measured at room temperature exhibits the clear FM with saturation magnetization (Ms) and coercive field (Hc) of the order of 3–7 emu/g a...

High temperature ferromagnetism and optical properties of Co doped ZnO nanoparticles

We report on the high temperature ferromagnetism of Co doped TiO2 nanoparticles (NPs) grown by a ball milling method with two different Co concentrations (3% and 8%). We also investigated the structural and optical properties of as-grown NPs to identify the defects which are responsible for the observed ferromagnetism (FM) at and above room temperature (RT). The obtained NPs of sizes 35–50 nm were identified as the anatase TiO2 structure with no signature of Co-cluster or any other oxides of Co by x-ray diffraction and high resolution transmission electron microscopy analysis. Raman scattering was employed to observe the defect related shifting and broadening of most intense Eg(1) mode at 142 cm−1 and higher frequency Eg(3) mode at 638 cm−1. UV-visible absorption spectra show that the incorporation of Co into the TiO2 lattice leads to redshift in the optical response, as well as lowering of bandgap energy. Photoluminescence study further confirms the doping of Co atoms into the TiO2 lattice as evidenced b...

Signature of strong ferromagnetism and optical properties of Co doped TiO2 nanoparticles

Structural, optical, and magnetic properties of Ni doped ZnO nanoparticles: Correlation of magnetic moment with defect density

Structural, optical and magnetic studies have been carried out for the Co-doped ZnO nanoparticles (NPs). ZnO NPs are doped with 3% and 5% Co using ball milling and ferromagnetism (FM) is studied at room temperature and above. A high Curie temperature (Tc) has been observed from the Co doped ZnO NPs. X-ray diffraction and high resolution transmission electron microscopy analysis confirm the absence of metallic Co clusters or any other phase different from wurtzite-type ZnO. UV-visible absorption and photoluminescence studies on the doped samples show change in band structure and oxygen vacancy defects, respectively. Micro-Raman studies of doped samples shows defect related additional strong bands at 547 and 574 cm(-1) confirming the presence of oxygen vacancy defects in ZnO lattice. The field dependence of magnetization (M-H curve) measured at room temperature exhibits the clear M-H loop with saturation magnetization and coercive field of the order of 4-6 emu/g and 260 G, respectively. Temperature dependence of magnetization measurement shows sharp ferromagnetic to paramagnetic transition with a high Tc = 791 K for 3% Co doped ZnO NPs. Ferromagnetic ordering is interpreted in terms of overlapping of polarons mediated through oxygen vacancy defects based on the bound magnetic polaron (BMP) model. We show that the observed FM data fits well with the BMP model involving localised carriers and magnetic cations.

Bappaditya Pal

Papers

High temperature ferromagnetism and optical properties of Co doped ZnO nanoparticles

Signature of strong ferromagnetism and optical properties of Co doped TiO2 nanoparticles

Structural, optical, and magnetic properties of Ni doped ZnO nanoparticles: Correlation of magnetic moment with defect density

Defect mediated magnetic interaction and high Tc ferromagnetism in Co doped ZnO nanoparticles.

Room temperature ferromagnetism with high magnetic moment and optical properties of Co doped ZnO nanorods synthesized by a solvothermal route