Water-hydroxide trapping in cobalt tungstate for proton exchange membrane water electrolysis.

The oxygen evolution reaction is the bottleneck to energy-efficient water-based electrolysis for the production of hydrogen and other solar fuels. In proton exchange membrane water electrolysis (PEMWE), precious metals have generally been necessary for the stable catalysis of this reaction. In this work, we report that delamination of cobalt tungstate enables high activity and durability through the stabilization of oxide and water-hydroxide networks of the lattice defects in acid. The resulting catalysts achieve lower overpotentials, a current density of 1.8 amperes per square centimeter at 2 volts, and stable operation up to 1 ampere per square centimeter in a PEMWE system at industrial conditions (80°C) at 1.77 volts; a threefold improvement in activity; and stable operation at 1 ampere per square centimeter over the course of 600 hours.

Ultra-Low-Loaded Platinum Bonded Hexagonal Boron Nitride as Stable Electrocatalyst for Hydrogen Generation.

Chemical stability of hexagonal boron nitride (hBN) ultrathin layers in harsh electrolytes and the availability of nitrogen site in hBN to stabilize metals like Pt are used here to develop a high intrinsic activity hydrogen evolution reaction (HER) catalyst having low loaded Pt (5 weight% or <1 atomic%). A catalyst having a nonzero oxidation state for Pt (with a Pt-N bonding) is shown to be HER active even with low catalyst loadings (0.114 mgcm-2). Electronic modification of the shear exfoliated hBN sheets is achieved by Au nanoparticle-based surface decoration (hBN_Au), and further anchoring with Pt develops a catalyst (hBN_Au_Pt) with high turnover frequency for HER (∼15). The hBN_Au_Pt is shown to be a highly durable catalyst even after the accelerated durability test for 10000 cycles and temperature annealing at 100 °C. Density functional theory based calculations gave insights in to the electronic modifications of hBN with Au and the catalytic activity of the hBN_Au_Pt system, in line with the experimental studies, indicating the demonstration of a new class of catalyst system devoid of issues such as carbon corrosion and Pt leaching.

Osmolytes as Cryoprotectants under Salt Stress.

Cryoprotecting agent (CPA)-guided preservation is essential for effective protection of cells from cryoinjuries. However, current cryoprotecting technologies practiced to cryopreserve cells for biomedical applications are met with extreme challenges due to the associated toxicity of CPAs. Because of these limitations of present CPAs, the quest for nontoxic alternatives for useful application in cell-based biomedicines has been attracting growing interest. Toward this end, here, we investigate naturally occurring osmolytes' scope as biocompatible cryoprotectants under cold stress conditions in high-saline medium. Via a combination of the simulation and experiment on charged silica nanostructures, we render first-hand evidence that a pair of archetypal osmolytes, glycine and betaine, would act as a cryoprotectant by restoring the indigenous intersurface electrostatic interaction, which had been a priori screened due to the cold effect under salt stress. While these osmolytes' individual modes of action are sensitive to subtle chemical variation, a uniform augmentation in the extent of osmolytic activity is observed with an increase in temperature to counter the proportionately enhanced salt screening. The trend as noted in inorganic nanostructures is found to be recurrent and robustly transferable in a charged protein interface. In hindsight, our observation justifies the sufficiency of the reduced requirement of osmolytes in cells during critical cold conditions and encourages their direct usage and biomimicry for cryopreservation.

Role of water structure in alkaline water electrolysis.

Herein, with the help of experimental and first-principles density functional theory (DFT)-based studies, we have shown that structural changes in the water coordination in electrolytes having high alkalinity can be a possible reason for the reduced catalytic activity of platinum (Pt) in high pH. Studies with polycrystalline Pt electrodes indicate that electrocatalytic HER activity reduces in terms of high overpotential required, high Tafel slope, and high charge transfer resistances in concentrated aqueous alkaline electrolytes (say 6 M KOH) in comparison to that in low alkaline electrolytes (say 0.1 M KOH), irrespective of the counter cations (Na+, K+, or Rb+) present. The changes in the water structure of bulk electrolytes as well as that in electrode-electrolyte interface are studied. The results are compared with DFT-based analysis, and the study can pave new directions in studying the HER process in terms of the water structure near the electrode-electrolyte interface.

Zwitterionic Osmolytes Revive Surface Charges under Salt Stress via Dual Mechanisms.

To counter the stress of a salt imbalance, the cell often produces low molecular weight osmolytes to resuscitate homeostasis. However, how zwitterionic osmolytes would tune the electrostatic interactions among charged biomacromolecular surfaces under salt stress has eluded mainstream investigations. Here, via combination of molecular simulation and experiment, we demonstrate that a set of zwitterionic osmolytes is able to restore the electrostatic interaction between two negatively charged surfaces that had been masked in the presence of salt. Interestingly, the mechanisms of resurrecting charge interaction under excess salt are revealed to be mutually divergent and osmolyte specific. In particular, glycine is found to competitively desorb the salt ions from the surface via its direct interaction with the surface. On the contrary, TMAO and betaine counteract salt stress by retaining adsorbed cations but partially neutralizing their charge density via ion-mediated interaction. These access to alternative modes of osmolytic actions would provide the cell the required flexibility in combating salt stress.

Study of the modified magnetic, dielectric, ferroelectric and optical properties in Ni substituted GdFe1-xNixO3orthoferrites.

Polycrystalline GdFe1-xNixO3(x = 0.00, 0.02, 0.04) samples was synthesised using a glycine assisted sol-gel method to investigate the enhanced magnetic and electric properties of Ni substituted GdFeO3systems. TG-DSC analysis of prepared samples confirms that GdFe1-xNixO3have good thermal stability in high temperatures. The system has been stabilized in an orthorhombic structure with space group Pbnm.The elemental composition of GdFe1-xNixO3has been estimated from EDAX spectrum. The results showed oxygen deficiency on increasing the Ni substitution and it has been supported by Rietveld refinement. FE-SEM images and Brunauer-Emmett-Teller analysis reveals that GdFe1-xNixO3is a highly porous material and its porosity and specific area increases with Ni substitution. Magnetic measurements indicates that the system exhibited ferrimagnetic behaviour at low temperatures and canted antiferromagnetic behaviour at room temperature. Forx = 0.04 Ni content, magnetization reversal for applied field of 25 Oe has been observed. Increased coercivity of GdFeO3with Ni substitution has been attributed to the grain size effect. From electrical point of view, dielectric permittivity of GdFeO3has been enhanced with Ni substitution. This enhancement has been attributed to the cumulative effects of hopping of Fe2+-Fe3+ions, grain-grain boundary contribution, and space charge polarization. The role of grain-grain boundary contribution is evident from electric modulus spectrum. The space charge effect has been realized in both impedance spectrum and dielectric loss. Temperature-dependent dielectric studies were conducted to understand the mechanisms and various aspects that contribute to the dielectric enhancement. A highly lossy capacitive nature in theP-Eloop also suggests space charge effects due to Ni substitution in Fe sites. Availability of free charge carrier concentration is correlated with the optical properties of GdFe1-xNixO3. The decrease of optical band gap (2.5-2.21 eV) on increasing Ni content suggests the increasing electronic contribution in the system.

Facile water oxidation by dinuclear mixed-valence CoIII/CoII complexes: the role of coordinated water.

Rational design of a catalyst using earth abundant transition metals that can facilitate the smooth O-O bond formation is crucial for developing efficient water oxidation catalysts. The coordination environment around the metal ion of the catalyst plays a pivotal role in this context. We have chosen dinuclear mixed-valence CoIIICoII complexes of the general formula of [CoIIICoII(LH2)2(X)(H2O)] (X = OAc or Cl) which bear a coordinated water molecule in the primary coordination sphere. We anticipated that the water molecule in the primary sphere can take part in the proton coupled electron transfer (PCET) mechanism which can accelerate the facile formation of the O-O bond under strong alkaline conditions (1 M NaOH). To understand the role of the coordinated water molecule we have generated an analogous complex, [CoIIICoII(LH2)2(o-vanillin)] (o-vanillin = 2-hydroxy-3-methoxybenzaldehyde), without coordinated water. Interestingly, we have found that the water coordinated complexes show better oxygen evolution reaction (OER) activity and stability.

A tetranuclear cobalt(ii) phosphate possessing a D4R core: an efficient water oxidation catalyst.

The reaction of Co(OAc)2·4H2O with a sterically hindered phosphate ester, LH2, afforded a tetranuclear complex, [CoII(L)(CH3CN)]4·5CH3CN (1) [LH2 = 2,6-(diphenylmethyl)-4-isopropyl-phenyl phosphate]. The molecular structure of 1 reveals that it is a tetranuclear assembly where the Co(ii) centers are present in the alternate corners of a cube. The four Co(ii) centers are held together by four di-anionic [L]2- ligands. The fourth coordination site on Co(ii) is taken by an acetonitrile ligand. Changing the Co(ii) precursor from Co(OAc)2·4H2O to Co(NO3)2·6H2O afforded a mononuclear complex [CoII(LH)2(CH3CN)2(MeOH)2](MeOH)2 (2). In 2, the Co(ii) centre is surrounded by two monoanionic [LH]- ligands and a pair of methanol and acetonitrile solvents in a six-coordinate arrangement. 1 has been found to be an efficient catalyst for electrochemical water oxidation under highly basic conditions while the mononuclear analogue, 2, does not respond to electrochemical water oxidation. The tetranuclear catalyst has excellent electrochemical stability and longevity, as established by chronoamperometry and >1000 cycle durability tests under highly alkaline conditions. Excellent current densities of 1 and 10 mA cm-2 were achieved with overpotentials of 354 and 452 mV respectively. The turnover frequency of this catalyst was calculated to be 5.23 s-1 with an excellent faradaic efficiency of 97%, indicating the selective oxygen evolution reaction (OER) occurring with the aid of this catalyst. A mechanistic insight into the higher activity of complex 1 towards the OER compared to that of complex 2 is also provided using density functional theory based calculations.