Giant electrostriction-like response from defective non-ferroelectric epitaxial BaTiO3 integrated on Si (100).

Lead-free, silicon compatible materials showing large electromechanical responses comparable to, or better than conventional relaxor ferroelectrics, are desirable for various nanoelectromechanical devices and applications. Defect-engineered electrostriction has recently been gaining popularity to obtain enhanced electromechanical responses at sub 100 Hz frequencies. Here, we report record values of electrostrictive strain coefficients (M31) at frequencies as large as 5 kHz (1.04×10-14 m2/V2 at 1 kHz, and 3.87×10-15 m2/V2 at 5 kHz) using A-site and oxygen-deficient barium titanate thin-films, epitaxially integrated onto Si. The effect is robust and retained upon cycling upto 6 million times. Our perovskite films are non-ferroelectric, exhibit a different symmetry compared to stoichiometric BaTiO3 and are characterized by twin boundaries and nano polar-like regions. We show that the dielectric relaxation arising from the defect-induced features correlates well with the observed giant electrostriction-like response. These films show large coefficient of thermal expansion (2.36 × 10-5/K), which along with the giant M31 implies a considerable increase in the lattice anharmonicity induced by the defects. Our work provides a crucial step forward towards formulating guidelines to engineer large electromechanical responses even at higher frequencies in lead-free thin films.

High entropy alloying strategy for accomplishing quintuple-nanoparticles grafted carbon towards exceptional high-performance overall seawater splitting.

High entropy alloys (HEAs), a novel class of material, have been explored in terms of their excellent mechanical properties. Seawater electrolysis is a step towards sustainable production of carbon-neutral fuels such as H2, O2, and industrially demanding Cl2. Herein, we report a practically viable FeCoNiMnCr HEA nanoparticles system grafted on a conductive carbon matrix for promising seawater electrolysis. The comprehensive kinetics analysis of the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and chlorine evolution reaction (CER) confirms the effectiveness of our system. As an electrocatalyst, HEAs grafted on carbon black show trifunctionality with promising kinetics, selectivity and enduring performance, towards seawater splitting. We optimize high entropy alloy decorated/grafted carbon black (HEACB) catalysts, studying their synthesis temperature to scrutinize the effect of alloy formation variation on the catalysis efficacy. During the catalysis, selectivity between two mutually competing reactions, CER and OER, in the electrochemical catalysis of seawater is controlled by the reaction media pH. We employ Mott-Schottky measurements to probe the band structure of the intrinsically induced metal-semiconductor junction in the HEACB catalyst, where the carrier density and flat band potential are optimized. The HEACB sample provides promising results towards overall seawater electrolysis with a net half-cell potential of about 1.65 V with good stability, which strongly implies its broad practical applicability.

Self-Assembled TMD Nanoparticles on N-Doped Carbon Nanostructures for Oxygen Reduction Reaction and Electrochemical Oxygen Sensing Thereof.

Here, we report on a universal carbothermal reduction strategy for the synthesis of well-dispersed WS2 nanoparticles (∼1.7 nm) supported on a N-doped carbon (NxC) nanostructure and the electrocatalytic activity toward oxygen reduction reaction (ORR). Bulk WS2 powder (2 µm) is the source for WS2 nanoparticles, and dicyandiamide is the source for NxC and carbothermal reduction. Interestingly, WS2/NxC serves the purpose of innovative and robust active sites for ORR through an efficient four-electron transfer process with excellent durability. Remarkably, WS2/NxC suppresses the peroxide generation due to the dominating inner-sphere electron transfer mechanism where the direct adsorption of the desolvated O2 molecule on the electroactive centers takes place. The mass activity (at 0.4 and 0.85 V vs RHE) of WS2/NxC outperforms the previously reported transition metal based electrocatalysts. The study further establishes a correlation between the work function and the ORR activity. We have also exploited WS2/NxC for electrochemical oxygen sensing, and there exists a direct correlation between oxygen sensing and ORR as both depend on the oxygen adsorption ability. Finally, the carbothermal reduction strategy has been extended for the synthesis of other TMDs/NxC such as MoS2/NxC, MoSe2/NxC, and WSe2/NxC.

Specific Absorption Rate Dependency on the Co2+ Distribution and Magnetic Properties in CoxMn1-xFe2O4 Nanoparticles.

Mixed ferrite nanoparticles with compositions CoxMn1-xFe2O4 (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) were synthesized by a simple chemical co-precipitation method. The structure and morphology of the nanoparticles were obtained by X-ray diffraction (XRD), transmission electron microscope (TEM), Raman spectroscopy, and Mössbauer spectroscopy. The average crystallite sizes decreased with increasing x, starting with 34.9 ± 0.6 nm for MnFe2O4 (x = 0) and ending with 15.0 ± 0.3 nm for CoFe2O4 (x = 1.0). TEM images show an edge morphology with the majority of the particles having cubic geometry and wide size distributions. The mixed ferrite and CoFe2O4 nanoparticles have an inverse spinel structure indicated by the splitting of A1g peak at around 620 cm-1 in Raman spectra. The intensity ratios of the A1g(1) and A1g(2) peaks indicate significant redistribution of Co2+ and Fe3+ cations among tetrahedral and octahedral sites in the mixed ferrite nanoparticles. Magnetic hysterics loops show that all the particles possess significant remnant magnetization and coercivity at room temperature. The mass-normalized saturation magnetization is highest for the composition with x = 0.8 (67.63 emu/g), while CoFe2O4 has a value of 65.19 emu/g. The nanoparticles were PEG (poly ethylene glycol) coated and examined for the magneto thermic heating ability using alternating magnetic field. Heating profiles with frequencies of 333.45, 349.20, 390.15, 491.10, 634.45, and 765.95 kHz and 200, 250, 300, and 350 G field amplitudes were obtained. The composition with x = 0.2 (Co0.2Mn0.8Fe2O4) with saturation magnetization 57.41 emu/g shows the highest specific absorption rate (SAR) value of 190.61 W/g for 10 mg/mL water dispersions at a frequency of 765.95 kHz and 350 G field strength. The SAR values for the mixed ferrite and CoFe2O4 nanoparticles increase with increasing concentration of particle dispersions, whereas for MnFe2O4, nanoparticles decrease with increasing the concentration of particle dispersions. SARs obtained for Co0.2Mn0.8Fe2O4 and CoFe2O4 nanoparticles fixed in agar ferrogel dispersions at frequency of 765.95 kHz and 350 G field strength are 140.35 and 67.60 W/g, respectively. This study shows the importance of optimizing the occupancy of Co2+ among tetrahedral and octahedral sites of the spinel system, concentration of the magnetic nanoparticle dispersions, and viscosity of the surrounding medium on the magnetic properties and heating efficiencies.

Shock Processing of Amino Acids Leading to Complex Structures-Implications to the Origin of Life.

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the 'threads' observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.