ABSTRACT
Despite the narrow band gap energy, the performance of zinc ferrite (ZnFe2O4) as a photoharvester for solar-driven water splitting is significantly hindered due to its sluggish charge transfer and severe charge recombination. This work reports the fabrication of a hybrid nanostructured hydrogenated ZnFe2O4 (ZFO) photoanode with enhanced photoelectrochemical water-oxidation activity through coupling N-doped graphene quantum dots (GQDs) as a hole transfer layer and Co-Pi as a catalyst. The GQDs not only reduce the surface-mediated nonradiative electron-hole pair recombination but also induce a built-in interfacial electric field leading to a favorable band alignment at the ZFO/GQDs interface, helping rapid photogenerated hole separation and serving as a conducting hole transfer highway, improve the hole transportation into the Co-Pi catalyst for enhanced water oxidation reaction kinetics. The optimized ZFO/GQD/Co-Pi hybrid photoanode delivers a 23-fold photocurrent enhancement at 1.23 V versus the reversible hydrogen electrode (RHE) and a significant 360 mV reduction in the onset potential, reaching 0.65 VRHE compared with the ZFO photoanode under 1 sun illumination in a neutral electrolytic environment. This investigation underscores the mechanism of synergistic interplay between the hole transport layer and cocatalyst in boosting the solar-illuminated water-splitting activity of the ZFO photoanode.
ABSTRACT
Gallium ferrite (GFO) is a magnetoelectric (ME) material, capturing growing attention due to its strong ME coupling at room temperature. However, the application of the material in practical use is hindered due to its high leakage. In this work, the effects of cobalt (Co) substitution at the iron (Fe) sites of GaFe1-xCoxO3(0.0 ⩽x⩽ 0.1) polycrystals on the structure, electric and magnetic properties are investigated in detail. 5 at. wt.% substitution (x= 0.05) with cobalt ions achieves a reduction in leakage current density by four orders of magnitude due to reduced hopping between Fe3+and Fe2+ions and suppression of the oxygen vacancy formation. This is supported by higher dielectric constant and lower dielectric loss, as well as a significant difference between grain and grain boundary resistances. Two-phase-like magnetic behavior in magnetic hysteresis loop with enhanced magnetization and two magnetic transition temperatures are observed in the doped samples. All samples exhibited an increase in the magnetodielectric factor, indicating enhanced coupling between magnetic and electrical parameters. By concurrently increasing dielectric, magnetic, and coupling between them, this study describes a viable technique for lowering the most significant impediment to GFO's usage as a ME device.
ABSTRACT
We report on the tuning of electrical, magnetic, and topological properties of the magnetic Weyl semimetal (Mn3+xGe) by Fe doping at the Mn site, Mn(3+x)-δFeδGe (δ= 0, 0.30, and 0.62). Fe doping significantly changes the electrical and magnetic properties of Mn3+xGe. The resistivity of the parent compound displays metallic behavior, the system withδ= 0.30 of Fe doping exhibits semiconducting or bad-metallic behavior, and the system withδ= 0.62 of Fe doping demonstrates a metal-insulator transition at around 100 K. Further, we observe that the Fe doping increases in-plane ferromagnetism, magnetocrystalline anisotropy, and induces a spin-glass state at low temperatures. Surprisingly, topological Hall state has been noticed at a Fe doping ofδ= 0.30 that is not found in the parent compound or withδ= 0.62 of Fe doping. In addition, spontaneous anomalous Hall effect observed in the parent system is significantly reduced with increasing Fe doping concentration.
ABSTRACT
Magnetic topological semimetals (TSMs) with broken time-reversal symmetry are very rare and have drawn significant attention in condensed matter physics due to their numerous intriguing topological properties. Among these various magnetic TSMs, Co2-based full Heusler compounds are of current interest, since a few of these materials exhibit Weyl and nodal fermions in their topological band structure. In this work, we report a comprehensive study of anomalous Hall effect (AHE) in the ferromagnetic full Heusler compound Co2VAl. Recent studies indicate that the intrinsic AHE is closely related to the Berry curvature of the occupied electronic Bloch states. The present study of Co2VAl attempts to understand and explore the possibility of topology-induced AHE. The anomalous Hall resistivityρxyAis observed to scale quadratically with the longitudinal resistivityρxx. Our experimental results also reveal that the anomalous Hall conductivity (AHC) is â¼85 cm-1at 2 K with an intrinsic contribution of â¼75.6 S cm-1, and is nearly insensitive to temperature. The first principle calculations note that the Berry curvature originated from a gapped nodal line and symmetry-protected Weyl nodes near the Fermi level (EF) is the main source of AHE in this compound. Thus, this investigation on Co2VAl discloses that it is a ferromagnetic Weyl and nodal-line TSM. The theoretically calculated AHC is in well agreement with the experimentally obtained AHC.
ABSTRACT
Hematite (α-Fe2O3) photoanode suffers from significant photocarrier recombination and sluggish water oxidation kinetics for photoelectrochemical water splitting. To address these challenges, this work demonstrates the construction of dual co-catalysts modified Fe2O3nanorods photoanode by strategically incorporating CoPi and Co(OH)xfor photoelectrochemical water oxidation. The Fe2O3/CoPi/Co(OH)xnanorods photoanode exhibits the lowest ever turn-on potential of 0.4VRHE(versus reversible hydrogen electrode) and a photocurrent density of 0.55 mA cm-2at 1.23VRHE, 358% higher than that of pristine Fe2O3nanorods. The dual co-catalysts modification enhances the light-harvesting efficiency, surface photovoltage and hole transfer kinetics of the hybrid photoanode. The dual co-catalyst coupling also increases the carrier density and significantly reduces the depletion width (1.9 nm), resulting in improved conductivity and favorable band bending, boosting photogenerated hole transfer efficiency for water oxidation.
ABSTRACT
We report a giant exchange bias (EB) field of about 3.68 kOe during field cooled process in all-d-metal Ni40(FeCo)4Mn36Ti20Heusler alloy. The study of magnetic memory effect and isothermal magnetic relaxation processes suggest that the giant EB field arises due to the possible coexistence of antiferromagnetic (AFM) and ferromagnetic (FM) phase exchange interaction in the studied system at temperatures below 35 K. Furthermore, the temperature and cooling field dependence of EB effect are analyzed which are related to the change in unidirectional anisotropy at FM/AFM interface. The study of a well-established training effect confirms the intrinsic nature of the observed EB behavior. This result will open up a new way toward the development of EB materials considering all-d-metal Heusler alloy systems.
ABSTRACT
In this work we have synthesized Mn doped GdFeO3 nano-particles using a green and facile sol gel method and studied their photocatalytic, optical, vibrational and electrical properties. The Rietveld refinement of the XRD profiles suggests that all the materials have an orthorhombic Pbnm crystal structure. The transmission electron microscope (TEM) images show the decrease of the average particle size from 140 to 80 nm with the Mn concentration. The high crystallinity of the synthesized particles is confirmed from the HR-TEM images. Raman spectrum is employed to investigate the phonon modes of the materials. The optical band gap of the materials is obtained from the UV-vis reflectance spectroscopy (DRS) using Tauc relation which indicates the reduction of the band gap from 2.18 to 1.72 eV with Mn-doping. The photocatalytic activity of the materials is studied by the photocatalytic degradation of rhodamine B (Rh-B) in aqueous solution under visible light illumination. The substitution of Mn at the Fe site introduces an extra electronic state between the conduction band and the valence band which reduces the electronic band gap and enhances the Rh-B degradation efficiency. A 30% Mn doping at the Fe site (GFMO3) provides an optimum space charge width which assists to attain the maximum rate of degradation of the Rh-B dye. The doping of Mn3+ reduces the photogenerated electron and hole recombination rate and hence more charge carriers take part in the redox reaction which facilitates the photo-catalytic efficiency in GFMO3. The degradation rate enhances by a factor of 2.5 for GFMO3 as compared to pure GdFeO3. The highest photocurrent density of 1.31 µA cm-2 of GFMO3 with respect to other materials promotes the separation and transfer of the photo generated charge carriers. The possible photocatalytic mechanism of the Mn doped GdFeO3 is also critically discussed. Alternating current impedance spectroscopy is used to study the electrical properties of the synthesized materials. The increase in the conductivity with the Mn concentration is explained on the basis of the band gap reduction and this is consistent with the Smit and Wijn theory. Magnetic measurement is performed to measure the magnetization strength which is useful to separate the photocatalyst by simply using a magnet. The temperature dependent magnetization measurement suggests the anti-ferromagnetic (AFM) behaviour of the studied materials with the decrease of Néel temperature (TN) with Mn concentration. The XPS study reveals the presence of multiple oxidation states of Fe(2+/3+) and Mn(4+/3+) in these materials which facilitates the conductivity as well as the oxidation/reduction efficiency at the surface of the catalyst. The band gap reduction and its effect on the enhancement of the photocatalytic degradation efficiency with Mn doping are also discussed from the density of states calculations. Thus, this study describes a promising approach for the organic pollutant degradation by designing an efficient and stable perovskite photocatalyst.
ABSTRACT
Ferrite nano-hollow spheres (NHS) are of great significance to improve electromagnetic (EM) wave absorption performance. Herein, the deposition of dielectric SiO2and ferrimagnetic CoFe2O4(CFO) layers on MnFe2O4(MnFO) NHS are found as an effective strategy to enhance EM wave attenuation. EM wave absorption properties of as-synthesized bare and bi-layered samples are investigated within a widely-used frequency range of 1-17 GHz. MnFO@CFO bi-layered NHSs exhibit an excellent reflection loss (RL) of -47.0 dB at only 20 wt% filler content with an effective broad bandwidth (BW) of â¼2.2 GHz (frequency region for RL < -10 dB). The attenuation constant is observed to increase from 191.6 Np m-1to 457.8 Np m-1for bare MnFO and MnFO@CFO NHSs respectively. Larger interfacial area, additional pairs of dipole, higher magnetic anisotropy, internal reflections and scattering from NHSs are responsible for superior absorption properties of MnFO@CFO NHSs. Moreover, the best impedance matching,â£Zin/Z0⣠⼠1, promotes the optimum RL in MnFO@CFO at 5.96 GHz. MnFO@SiO2bi-layered NHSs result in a sufficiently high RL â¼ -30.0 dB with a composite absorber of a thickness of only 3 mm. Analysis from theλ/4 model for best matching thickness (tm) displays a good agreement between experimental and simulatedtmvalues. This study demonstrates optimized MnFO@CFO NHS as a highly promising low-cost and lightweight EM wave absorber suitable for practical high-frequency applications.
ABSTRACT
Poor light absorption, severe surface charge recombination and fast degradation are the key challenges with ZnO nanostructures based electrodes for photoelectrochemical (PEC) water splitting. Here, this study attempts to design an efficient and durable nano-heterojunction photoelectrode by integrating earth abundant chemically stable transition metal spinel ferrites MFe2O4 (M = Co and Ni) nano-particles on ZnO Nanorod arrays. The low band gap magnetic ferrites improve the solar energy harvesting ability of the nano-heterojunction electrodes in ultraviolet-visible light region resulting in a maximum increase of 105% and 190% in photocurrent density and applied bias photon-to-current efficiency, respectively, compared to pristine ZnO nanorods. The favourable type-II band alignment at the ferrites/ZnO nano-heterojunction provides significantly enhanced photo-generated carrier separation and transfer, endowing the excellent solar H2 evolution ability (743 and 891 µmol cm-2 h-1for ZnO/CoFe2O4 and ZnO/NiFe2O4, respectively) of the photoanodes by using sacrificial agent. The hybrid nanostructures deliver long term stability of the electrode against photocorrosion. This work demonstrates an easy but effective strategy to develop low-cost earth abundant ferrites-based heterojunction electrodes, which offers excellent PEC activity and stability.
ABSTRACT
Carbon monoxide (CO), being a highly toxic gas, bears hazardous effects on human health and contributes majorly to environmental pollution. It is mostly produced by automobile exhausts and incomplete combustion of carbon-containing substances. Thus, the development of catalysts for CO conversion is highly imperative and has always gained interest for real field applications. Besides the high oxygen storage capacity and facile transitions between oxidation states, the huge abundance of cerium on earth makes CeO2 a low-cost and highly effective alternative to noble metal catalysts for CO oxidation. The present work delineates the room temperature synthesis of flower-shaped 3D CeO2 nanostructures using a sonication-assisted simple synthesis method within 2 hours under the pivotal importance of a structure-directing agent, polyvinylpyrrolidone (PVP). The bifunctional contributions of PVP as a surfactant and as a capping agent are discussed with a plausible mechanism. The method leading to the formation of hierarchical CeO2 nanoflowers provides an appreciable surface area of 132.69 cm2 g-1. The morphological and structural characterizations of the catalyst were thoroughly investigated using FESEM, TEM, XRD, UV-visible spectroscopy, photoluminescence spectroscopy, FTIR spectroscopy and X-ray photoelectron spectroscopy. The structural efficacies of flower-like CeO2 nanostructures have also been correlated to the narrowing of the band gap and the generation of the corresponding oxygen vacancies, resulting in surface catalytic properties towards 80% conversion of CO.
ABSTRACT
This work comprises the shape- and facet-dependent catalytic efficacies of different morphologies of CeO2, namely, hexagonal, rectangular, and square. The formation of different shapes of CeO2 is controlled using polyvinyl pyrrolidone as a surfactant. The surface reactivity of formation of differently exposed CeO2 facets is thoroughly investigated using UV-visible, photoluminescence, Raman, and X-ray photoelectron spectroscopies. A correlation between the growth of a surface-reactive facet and the corresponding oxygen vacancies is also established. Considering the tremendous contamination, caused by the textile effluents, the present study articulates the facet-dependent photocatalytic activities of pristine CeO2 for complete degradation of methylene blue within 175 min. The observed degradation time deploying pristine CeO2 as a catalyst is the shortest to be reported in the literature to our best knowledge.
ABSTRACT
The emerging category of magneto-fluorescent tartrate-modified MnFe2O4 nano hollow spheres (T-MnFe2O4 NHSs) can be considered as promising candidates for biomedical applications. The interaction of bovine serum albumin (BSA) with T-MnFe2O4 NHSs has been studied using several spectroscopic techniques, which suggest that the interaction occurs by an electrostatic mechanism. Furthermore, BSA enhances the charge transfer transition from the tartrate ligand to the metal ions along with the d-d transition of Fe3+ ions on NHSs surfaces at different pH. Very strong salt bridge formation occurs between the lysine of the BSA surface and the tartrate in basic medium (pH 10), followed by the acidic (pH 3) and neutral medium (pH 7), respectively. Systematic fluorescence microscopic analysis reveals that BSA significantly enhances the contrast of T-MnFe2O4 NHSs in UV and blue light excitation because of the extended charge transfer from BSA to T-MnFe2O4 NHSs. Our report demonstrates great potential in the field of nanotechnology and biomedical applications. In vitro toxicity analysis using RAW 264.7 celline and in vivo studies on Wister rats revealed that the T-MnFe2O4 NHSs are benign. Furthermore, T-MnFe2O4 NHSs also appear to be an antimicrobial agent. Therefore, T-MnFe2O4 NHSs can be explored for future therapeutic applications.
Subject(s)
Ferric Compounds/chemistry , Manganese Compounds/chemistry , Nanospheres/chemistry , Serum Albumin, Bovine/chemistry , Spectrometry, Fluorescence , Tartrates/chemistry , Animals , Cell Survival/drug effects , Ferric Compounds/toxicity , Fluorescence , Mice , Nanospheres/toxicity , RAW 264.7 Cells , RatsABSTRACT
Herein, we report the observation of unusual electronic and magnetic phases in traditional antiferromagnetic Co3O4 micromaterials and modulation of their properties on a temperature scale. In particular, we demonstrate a comparative low-energy carrier dynamics of Co3O4 microflower and microhollow flower (MHF) structures of same average size of 2 µm to unravel the ground-state information induced by surface electronics across the insulator-semiconductor transition using terahertz (THz) time domain spectroscopy. Interestingly, the THz optical constants of these structures are found to exhibit remarkably distinct features both as a function of frequency and temperature. Detailed study reveals that the partial metallization through large two-dimensional surface electronic states of MHF structure enables to achieve significantly higher carrier dynamics in contrast to its wide-band-gap solid counterparts and the magnetic measurements reconfirm the presence of these surface states by indicating ferromagnetism in Co3O4 MHF structures. Moreover, the simultaneous existence of insulator-semiconductor and antiferromagnetic-paramagnetic transitions near the Néel temperature points out the significant role of magnetically active Co2+ ions at the tetrahedral site of Co3O4 normal spinel structure in determining the conduction dynamics instead of 3d band related to Co3+ ions at octahedral site. Finally, we demonstrate that the continuous modulation of temperature-controlled charge transport coupled with intrinsic phase transition in Co3O4 microstructures has the potential to design efficient analog-like THz modulator, filter, and sensor. We believe that these outcomes can stimulate new opportunities toward next-generation caloritronics-based ultrafast energy-efficient transition-metal oxide electronics having both economic and environmental significance.
ABSTRACT
The effective utilization of abundant visible solar light for photoelectrochemical water splitting is a green approach for energy harvesting, to reduce the enormous rise of carbon content in the atmosphere. Here, a novel efficient design strategy for p-n type nano-heterojunction photoanodes is demonstrated, with the goal of improving water splitting efficiency by growing low band gap p-CuFeO2 nanolayers on n-ZnO nanorods by an easy and scalable electrochemical route. The photoconversion efficiency of p-n CuFeO2/ZnO photoanodes is found to be â¼450% higher than that of pristine ZnO nanorod electrodes under visible solar light illumination (λ > 420 nm, intensity 10 mW cm-2). The p-n CuFeO2/ZnO nano-engineering not only boosts the visible light absorption but also resolves limitations regarding effective charge carrier separation and transportation due to interfacial band alignment. This photoanode also shows remarkably enhanced stability, where the formation of p-n nano-heterojunction enhances the easy migration of holes to the electrode/electrolyte interface, and of electrons to the counter electrode (Pt) for hydrogen generation. Therefore, this work demonstrates that p-n nano-engineering is a potential strategy to design light-harvesting electrodes for water splitting and clean energy generation.
ABSTRACT
This article demonstrates comprehensive studies on different visible-light driven photoelectrochemical and photocatalytic aspects of a hydrothermally synthesized n-type H2Ti3O7 (HTO) nanowire mesh and its carbon and nitrogen functionalized counterparts, namely C-HTO and N-HTO. It was found that the presence of various defect states within the band gap of HTO, C-HTO and N-HTO nanowires, make them photoactive under visible-light. The photo-conversion efficiencies of HTO, C-HTO, and N-HTO nanowire electrodes are about 0.066, 0.129, and 0.076%, respectively, at around 1 V vs. Ag/AgCl. Carbon functionalization of HTO nanowires has been found to be most beneficial in increasing the charge carrier density, resulting in the highest current density, high photo conversion efficiency, remarkable photoelectrochemical water splitting performance and enhanced photocatalytic activity. The photocurrent density of the C-HTO NWs was found to be 0.0562 mA cm-2 at 1 V vs. Ag/AgCl, which is almost two times that of the pristine HTO NWs (0.029 mA cm-2). Although nitrogen functionalization increases the charge carrier density of the HTO nanowires, nitrogen incorporation produces lots of recombination centres in the nanowires, which are found to play a detrimental role in the photoelectrochemical and photocatalytic performance of N-HTO nanowires, limiting the expected performance. Therefore, the present study demonstrates a suitable surface engineering technique for nanostructures to maximize the utilization of green solar light.
ABSTRACT
1D Permalloy refers to arrays of nanowires (NWs) made of an alloy of Ni and Fe with 80 and 20 at% composition respectively. In the present work 1 D Permalloy NWs arrays were fabricated into the pores of self engineered Anodic Aluminium Oxide (AAO) templates by a simple electrodeposition technique (EDT). By varying the anodization voltage and parameters of the electrolyte solutions we developed AAO templates with different average pore diameters (40 nm to 70 nm) and developed 1D Permalloy NWs within them. Structural characterization of AAO templates and 1D Permalloy NWs were performed by Transmission and Scanning Electron Microscopy (TEM and SEM respectively). X-ray diffraction (XRD) studies of 1D Permalloy NWs showed their fcc crystalline structure and the AAO template was found to be amorphous in nature. Magnetic studies showed the 1D Permalloy NWs arrays to have strong shape anisotropy, and the easy axis was found to be parallel to the NWs axis. We studied the angular dependence of magnetic properties of the NWs. Coercivity (Hc) and remanence (Mr/Ms) measured along the NWs axis were found to be higher than those measured in a direction perpendicular to the NWs axis. 1D Permalloy NWs developed in this work have the potential to be used in magnetic recording devices.
ABSTRACT
We report a facile method to design Co3O4-MnO2-NiO ternary hybrid 1D nanotube arrays for their application as active material for high-performance supercapacitor electrodes. This as-prepared novel supercapacitor electrode can store charge as high as â¼2020 C/g (equivalent specific capacitance â¼2525 F/g) for a potential window of 0.8 V and has long cycle stability (nearly 80% specific capacitance retains after successive 5700 charge/discharge cycles), significantly high Coulombic efficiency, and fast response time (â¼0.17s). The remarkable electrochemical performance of this unique electrode material is the outcome of its enormous reaction platform provided by its special nanostructure morphology and conglomeration of the electrochemical properties of three highly redox active materials in a single unit.
ABSTRACT
To develop CoFe(2)O(4) as magneto-fluorescent nanoparticles (NPs) for biomedical applications, it would be advantageous to identify any intrinsic fluorescence of this important magnetic material by simply adjusting the surface chemistry of the NPs themselves. Herein, we demonstrate that intrinsic multicolor fluorescence, covering the whole visible region, can be induced by facile functionalization of CoFe(2)O(4) NPs with Na-tartrate. Moreover, the functionalized CoFe(2)O(4) NPs also show unprecedented catalytic efficiency in the degradation of both biologically and environmentally harmful dyes, pioneering the potential application of these NPs in therapeutics and wastewater treatment. Detailed investigation through various spectroscopic tools unveils the story behind the emergence of this unique optical property of CoFe(2)O(4) NPs upon functionalization with tartrate ligands. We believe our developed multifunctional CoFe(2)O(4) NPs hold great promise for advanced biomedical and technological applications.
Subject(s)
Cobalt/chemistry , Ferric Compounds/chemistry , Metal Nanoparticles/chemistry , Catalysis , Fluorescence , Ligands , Magnetics , Microscopy, Electron, TransmissionABSTRACT
Arrays of permalloy nanowires (NWs) were fabricated into the pores of self-engineered Anodic Aluminium Oxide (AAO) templates by a simple electrodeposition technique (EDT) with a diameter -200 nm. By varying the length of the nanowires from 1.5 to 7.5 microm, got corresponding changes in aspect ratio from 7.5 to 37.5. We studied the growth and structural properties of permalloy nanowires using scanning electron microscopy, X-ray diffraction spectra and transmission electron microscopy. We performed the magnetic measurements of permalloy nanowires using vibrating sample magnetometer. The coercivity (H(c)) and anisotropy field (H(an)) observed considerably higher when the applied magnetic field was perpendicular to the nanowires axial direction (In-Plane) compare to the applied magnetic field was parallel to the nanowire axial direction (Out-of-plane). Reverse trend was observed for the maximum remanent ratio (M(r)/M(s)). So we concluded that the magnetic easy axis of the permalloy nanowires are along the axial direction of the nanowires and magnetic hardness of the nanowires higher in transverse direction compare to the axial direction of nanowires. For the first time temperature (80 K < or = T < or = 300 K) and aspect ratio dependence magnetic properties of the permalloy nanowires have been studied in detail.
ABSTRACT
Here solvo-thermal technique has been used to synthesize hollow-nanospheres of magnetite. We have shown that PVP plays an important role to control the particle size and also helps the particles to take the shape of hollow spheres. Structural analysis was done by XRD measurement and morphological measurements like SEM and TEM were performed to confirm the hollow type spherical particles formation and their shape and sizes were also investigated. The detail ac-dc magnetic measurements give an idea about the application of these nano spheres for hyperthermia therapy and spontaneous dye adsorption properties (Gibbs free energy deltaG0 = -0.526 kJ/mol for Eosin and -1.832 kJ/mol for MB) of these particles indicate its use in dye manufacturing company. Being hollow in structure and magnetic in nature such materials will also be useful in other application fields like in drug delivery, arsenic and heavy metal removal by adsorption technique, magnetic separation etc.