Investigation of Photoelectrocatalytic and Magnetic Properties of Sr2YbRu1-xTaxO6 (x = 0, 0.25, 0.5, 0.75, and 1).

We report the effect of substitution of Ru by Ta in Sr2YbRuO6 on its magnetic and photoelectrocatalytic properties. The powder X-ray diffraction data, was satisfactorily refined in the monoclinic space group, P21/n. The DC magnetization studies indicated that Sr2YbRuO6 shows antiferromagnetic interaction through Yb-O-Ru orbital ordering, with the highest Weiss temperature, among Sr2YbRu1-xTaxO6 (x = 0, 0.25, 0.5, and 0.75) which have values of -148, -125, -118, and -102 K, respectively. The difference in observed and theoretical magnetic moments was found to increase as x increases. It was also observed that with the increase of Ta concentration in Sr2YbRu1-xTaxO6, the band gap increased almost linearly, from 1.78(1) eV (x = 0) to 2.08(1) (x = 0.75), and thereafter a sharp increase 2.65(1) eV (x = 1) was observed, with the lowering of energy level of valence band, along with disruption in orbital ordering as x increases. The photoelectrocatalytic oxygen evolution reaction (OER) studies carried out on the series yield a maximum photocurrent density of 17 µA/cm2 and photoresponse current of 5.5 µA/cm2 at 0.8 V at an onset potential at 0.29 V vs Ag/AgCl for Sr2YbRuO6. The XPS analysis showed Ta and Ru to be in +5/+4 oxidation states, with the highest concentration of Ru4+ ion observed for Sr2YbRuO6. The presence of oxygen vacancies was confirmed by XPS as well as EPR studies.

Assessment of Performance of Photocatalytic Nanostructured Materials with Varied Morphology Based on Reaction Conditions.

Synthesis of nanomaterials with specific morphology is an essential aspect for the optimisation of its properties and applications. The application of nanomaterials is being discussed in a wide range of areas, one of which is directly relevant to the environment through photocatalysis. To produce an effective photocatalyst for environmental applications, morphology plays an important role as it affects the surface area, interfaces, crystal facets and active sites, which ultimately affects efficiency. The method of synthesis and synthesis temperature can be the basic considerations for the evaluation of a particular nanomaterial. In this study, we have considered the aspects of morphology with a basic understanding and analyzed them in terms of nanomaterial efficacy in photocatalysis. Different morphologies of specific nanomaterials such as titanium dioxide, zinc oxide, silver phosphate, cadmium sulphide and zinc titanate have been discussed to come to reasonable conclusions. Morphologies such as nanorods, nanoflower, nanospindles, nanosheets, nanospheres and nanoparticles were compared within and outside the domain of given nanomaterials. The different synthesis strategies adopted for a specific morphology have been compared with the photocatalytic performance. It has been observed that nanomaterials with similar band gaps show different performances, which can be linked with the reaction conditions and their nanomorphology as well. Materials with similar morphological structures show different photocatalytic performances. TiO2 nanorods appear to have the best features of efficient photocatalyst, while the nanoflowers show very low efficiency. For CdS, the nanoflower is the best morphology for photocatalysis. It appears that high surface area is the key apart from the morphology, which controls the efficiency. The overall understanding by analyzing all the available information has enumerated a path to select an effective photocatalyst amongst the several nanomaterials available. Such an analysis and comparison is unique and has provided a handle to select the effective morphology of nanomaterials for photocatalytic applications.

Continuous Flow Reactor for the Controlled Synthesis and Inline Photocatalysis of Antibacterial Ag2 S Nanoparticles.

The present study is focused on the integration of microreactors to synthesize visible light active nanophotocatalysts for inline photocatalytic degradation of organic dye and antibacterial activity. A wire-assisted and a rapid laser micromachining technique has been employed for the fabrication of polydimethylsiloxane (PDMS) and poly(methyl methacrylate) (PMMA)-based microreactors, respectively. By varying the design and chemical reagents involved, different sizes of visible light active Ag2 S nanoparticles were prepared via a continuous microfluidics approach using fabricated microreactors. When polyvinylpyrrolidone (PVP) was utilized as the capping agent during the reaction, smaller particles of the size of ~ 15 nm were observed. The photocatalytic performance of these nanoparticles has been evaluated inline by employing the single-inlet planar microreactor as a function of flow rate and channel length. The photocatalyst durability test and a comparative photocatalytic efficiency study between the microreactor and the conventional beaker reactor have also been carried out. Under visible light, these nanoparticles exhibit a remarkable enhancement of ~ 94.5% in the inline microreactor-based photocatalytic degradation of methylene blue dye. The slower the flow rate and longer the channel length, gradual enhancement in the performance has been observed. Also, these nanoparticles express an antibacterial effect with very high efficacy even at very low (2 mg mL-1 ) concentration toward the inhibition of Escherichia Coli.

Core-Shell Type Semiconducting Heterostructures for Visible Light Photocatalysis.

This personal account highlights a part of the work done over the years in our group towards directed synthesis of morphologically controlled nanostructures. We begin with our efforts on the synthesis of families of nanostructured metal oxides and metal oxalates of well-defined morphology using low temperature microemulsion and hydrothermal techniques. The parameters that govern the morphology in these syntheses e. g. choice of solvent and temperature are described. We then discuss nanostructures with core-shell architecture and specifically their utilization to harvest visible light for photocatalysis and photoelectrochemical applications. The techniques described to utilize visible light include sensitizing wide bandgap semiconductors using 1) appropriate narrow bandgap materials and 2) metals that have surface plasmon resonance active bands. The reports are classified according to morphology with spherical, cubes and rods discussed in separate sections. A discussion of recent reports by other groups on core-shell structures of similar composition as well as future directions and perspectives are presented at the end.

Energy efficient electrodes for lithium-ion batteries: Recovered and processed from spent primary batteries.

In an attempt to develop low cost, energy efficient and advanced electrode material for lithium-ion batteries (LIBs), waste-to-wealth derived as well as value added spent battery materials as potential alternatives assume paramount importance. By combining the low lithiation potential advantages, one can arrive at energy efficient electrodes bestowed with cost effective and eco-friendly benefits required for practical LIB applications. In the present study, Zn and Mn-salts along with C were successfully extracted from the spent zinc carbon batteries through a simple and efficient hydrometallurgy approach and decomposed thermally to obtain ZnMn2O4 at 350 °C for 12 h and 450 °C for 3 h. Further, C-ZnMn2O4 nanocomposites were prepared and demonstrated for appreciable electrochemical performance in LIB assembly. Our results show that C-ZnMn2O4 composites prepared at 350 °C and 450 °C demonstrate better performance than pristine ZnMn2O4 anode due to the improved electronic conductivity rendered by the added carbon obtained from spent primary battery. In particular, C-ZnMn2O4 at 350 °C @12 h exhibits appreciable electrochemical performance by showing a stable and higher capacity of 600 mAhg-1 at a current density of 50 mAg-1 in the voltage range of 0.01-3.0 V and qualifies it as a better performing cost-effective anode for LIBs.

New approach for the transformation of metallic waste into nanostructured Fe3O4 and SnO2-Fe3O4 heterostructure and their application in treatment of organic pollutant.

Appropriate recycling of waste to reusable materials is much sought after in the scientific community to control the incessant rising pollution in environment due to insufficient management of waste materials. To address this issue, efforts were directed to obtain SnO2-Fe3O4 nanocomposites from scrap tin plated steel and the use of these composites for the degradation of organic pollutant. We have demonstrated a novel, efficient and facile hydrometallurgy approach for the extraction of iron from waste tin plated steel containers found in plenty in the common waste generated in society. The extracted iron has further been utilized for the preparation of SnO2:Fe3O4 nanocomposites with different compositions (SnO2:Fe3O4 ratio of 93.2:6.8, 85:15, 58:42 and 40:60) using hydrothermal route. The photocatalytic activities of nanocomposite were determined spectroscopically using Rhodamine-B (RhB) as a model dye. Our results indicate that among all the composites with SnO2 (85%):Fe3O4 (15%) exhibits the best photocatalytic efficiency under UV light whereas the composition of SnO2 (93.2%):Fe3O4 (6.28%) is the most efficient in visible light. The above visible light efficiency was supported by density functional theory (DFT) studies which suggest a small amount of pure Fe is present at the Sn sites in the nanocomposite, leading to the reduction in the band gap of the nanocomposite and resulting in absorption in the visible range. Thus, in the present study, we have shown a process of conversion of waste to nanomaterials and its utilization for treatment of organic pollutants.

Valence State of Eu and Superconductivity in Se-Substituted EuSr2Bi2S4F4 and Eu2SrBi2S4F4.

Recently, we reported the synthesis and investigations of EuSr2Bi2S4F4 and Eu2SrBi2S4F4. We have now been able to induce superconductivity in EuSr2Bi2S4F4 by Se substitution at the S site (isovalent substitution) with Tc = 2.9 K in EuSr2Bi2S2Se2F4. The other compound, Eu2SrBi2S4F4, shows a significant enhancement of Tc. In Se-substituted Eu2SrBi2S4-xSexF4, we find Tc = 2.6 K for x = 1.5 and Tc = 2.8 K for x = 2, whereas Tc = 0.4 K in the Se-free sample. In addition to superconductivity, an important effect associated with Se substitution is that it gives rise to remarkable changes in the Eu valence. Our 151Eu Mössbauer and X-ray photoemission spectroscopic measurements show that Se substitution in both of the compounds Eu2SrBi2S4F4 and EuSr2Bi2S4F4 gives rise to an increase in the Eu2+ component in the mixed-valence state of Eu.

Design of diverse nanostructures by hydrothermal and microemulsion routes for electrochemical water splitting.

Hydrothermal and microemulsion methods are low temperature methods used to obtain nanostructures of definite morphologies, sizes, facet termination and other structural features which result in the corresponding unique response to chemical, electrochemical or photochemical stimuli. An efficient catalyst to electrochemically split water to produce hydrogen and oxygen is of scientific, economic and societal relevance, especially due to the abundance of the starting material, water, and due to the product hydrogen, which is an ideal fuel, due to its highest mass density and clean combustion in air. In this review we focus on the hydrogen evolution reaction, HER, and the oxygen evolution reaction, OER, activity of the electrocatalysts produced by hydrothermal or microemulsion methods. The variation in electrochemical response resulting from the unique shape, composition and nano-architecture is discussed. Broadly, the catalysts were categorized as binary and ternary metal alloys as well as metal chalcogenides and oxides. This compilation would aid in the design of more effective water splitting electrocatalysts as well as in the selection of appropriate candidates for advanced mechanistic studies.

Pr2FeCrO6: A Type I Multiferroic.

We synthesized double perovskite Pr2FeCrO6 by solid-state method. Analysis of its X-ray powder diffraction shows that the compound crystallizes in a centrosymmetric structure with space group Pbnm. Our X-ray photoelectron spectroscopy (XPS) studies show that all the cations are present in +3 oxidation state. Magnetization studies of Pr2FeCrO6 show that the material is paramagnetic at room temperature and undergoes a magnetic transition below TCM = 250 K. We observe clear magnetic hysteresis loop, for example, below 150 K. A low remnant magnetization Mr, ∼0.05 µB/f. u., is inferred from the observed magnetic hysteresis loop. 57Fe Mössbauer study at 25 K shows a high hyperfine magnetic field of ∼53 T at the Fe nucleus, which corresponds to a magnetic moment of ∼6-7 µB/Fe. These two results together suggest a ferrimagnetic (nearly compensated or canted) ordering of the Fe moments. Mössbauer studies close to the ferrimagnetic ordering temperature suggest interesting magnetic relaxation effects. A dielectric anomaly observed at TCE = 453 K signals a ferroelectric ↔ paraelectric phase transition. We observe at room temperature a clear and well-defined ferroelectric hysteresis loop, PS = 1.04 µC/cm2, establishing ferroelectricity in the material. From these results, we conclude that Pr2FeCrO6 is a type I multiferroic (TCE > TCM).

Unusual Mixed Valence of Eu in Two Materials-EuSr2Bi2S4F4 and Eu2SrBi2S4F4: Mössbauer and X-ray Photoemission Spectroscopy Investigations.

We have synthesized two new Eu-based compounds, EuSr2Bi2S4F4 and Eu2SrBi2S4F4, which are derivatives of Eu3Bi2S4F4, an intrinsic superconductor with Tc = 1.5 K. They belong to a tetragonal structure (SG: I4/mmm, Z = 2), similar to the parent compound Eu3Bi2S4F4. Our structural and 151Eu Mössbauer spectroscopy studies show that, in EuSr2Bi2S4F4, Eu-atoms exclusively occupy the crystallographic 2a-sites. In Eu2SrBi2S4F4, 2a-sites are fully occupied by Eu-atoms and the other half of Eu-atoms and Sr-atoms together fully occupy 4e-sites in a statistical distribution. In both compounds Eu atoms occupying the crystallographic 2a-sites are in a homogeneous mixed valent state ∼2.6-2.7. From our magnetization studies in an applied H ≤ 9 T, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift toward 2+. Our XPS studies corroborate the occurrence of valence fluctuations of Eu and after Ar-ion sputtering show evidence of enhanced population of Eu2+-states. Resistivity measurements, down to 2 K, suggest a semimetallic nature for both compounds.

Synthesis and properties of SmO0.5F0.5BiS2 and enhancement in Tc in La1-ySmyO0.5F0.5BiS2.

The crystal structure and properties of a new member of the oxybismuth sulfide family SmO(0.5)F(0.5)BiS(2) are reported here. The compounds SmO(1-x)F(x)BiS(2) (x = 0.0 and 0.5) are isostructural with LaOBiS(2) and crystallize in the CeOBiS(2)-type structure (P4/nmm). Sm substitution in LaO(0.5)F(0.5)BiS(2) (La1-ySmyO(0.5)F(0.5)BiS(2)) leads to a gradual decrease in the a-lattice constant; however, the c-lattice constant does not show such a gradual trend. Enhancement in T(c) is achieved upon partial substitution of La by the smaller Sm ion. A maximum T(c) ∼ 4.6 K was observed for composition with y = 0.8. Disobeying this trend, Tc disappears unexpectedly in the composition SmO(0.5)F(0.5)BiS(2) (y = 1.0). Both the undoped and F-doped (x = 0.0 and 0.5) compounds are paramagnetic, exhibiting semiconducting behavior down to 2 K.

Enhanced functionalization of Mn2O3@SiO2 core-shell nanostructures.

Core-shell nanostructures of Mn2O3@SiO2, Mn2O3@amino-functionalized silica, Mn2O3@vinyl-functionalized silica, and Mn2O3@allyl-functionalized silica were synthesized using the hydrolysis of the respective organosilane precursor over Mn2O3 nanoparticles dispersed using colloidal solutions of Tergitol and cyclohexane. The synthetic methodology used is an improvement over the commonly used post-grafting or co-condensation method as it ensures a high density of functional groups over the core-shell nanostructures. The high density of functional groups can be useful in immobilization of biomolecules and drugs and thus can be used in targeted drug delivery. The high density of functional groups can be used for extraction of elements present in trace amounts. These functionalized core-shell nanostructures were characterized using TEM, IR, and zeta potential studies. The zeta potential study shows that the hydrolysis of organosilane to form the shell results in more number of functional groups on it as compared to the shell formed using post-grafting method. The amino-functionalized core-shell nanostructures were used for the immobilization of glucose and L-methionine and were characterized by zeta potential studies.