CoCrFeNi High-Entropy Alloy as an Enhanced Hydrogen Evolution Catalyst in an Acidic Solution.

High-entropy alloys (HEAs) have intriguing material properties, but their potential as catalysts has not been widely explored. Based on a concise theoretical model, we predict that the surface of a quaternary HEA of base metals, CoCrFeNi, should go from being nearly fully oxidized except for pure Ni sites when exposed to O2 to being partially oxidized in an acidic solution under cathodic bias, and that such a partially oxidized surface should be more active for the electrochemical hydrogen evolution reaction (HER) in acidic solutions than all the component metals. These predictions are confirmed by electrochemical and surface science experiments: the Ni in the HEA is found to be most resistant to oxidation, and when deployed in 0.5 M H2SO4, the HEA exhibits an overpotential of only 60 mV relative to Pt for the HER at a current density of 1 mA/cm2.

Modifying Metastable Sr1-xBO3-δ (B = Nb, Ta, and Mo) Perovskites for Electrode Materials.

The presence of surface/deep defects in 4d- and 5d-perovskite oxide (ABO3, B = Nb, Ta, Mo, etc.) nanoparticles (NPs), originating from multivalent B-site cations, contributes to suppressing their metallic properties. These defect states can be removed using a H2/Ar thermal treatment, enabling the recovery of their electronic properties (i.e., low electrical resistivity, high carrier concentration, etc.) as expected from their electronic structure. Therefore, to engineer the electronic properties of these metastable perovskites, an oxygen-controlled crystallization approach coupled with a subsequent H2/Ar treatment was utilized. A comprehensive study of the effect of the post-treatment time on the electronic properties of these perovskite NPs was performed using a combination of scattering, spectroscopic, and computational techniques. These measurements revealed that a metallic-like state is stabilized in these oxygen-reduced NPs due to the suppression of deep rather than surface defects. Ultimately, this synthetic approach can be employed to synthesize ABO3 perovskite NPs with tunable electronic properties for application into electrochemical devices.

Deep Eutectic Solvents Mixed with Fluorinated Refrigerants for Absorption Refrigeration: A Molecular Simulation Study.

Molecular simulations were performed to evaluate mixtures of fluorinated refrigerants with deep eutectic solvents (DESs), for potential use in single-effect absorption refrigeration cycles that use low quality waste heat sources at temperatures of ∼80 °C. The refrigerants considered were the hydrofluorocarbon R245fa and the hydrofluoroolefins R1234zeE and HFO1336mzzE, whereas the DESs evaluated were 1:2 molar mixtures of choline chloride with either ethylene glycol (ethaline) or levulinic acid (levuline) as hydrogen bond donors (HBDs). Assuming the same cycle operating conditions, the waste heat cycle efficiency η was computed for all working fluid mixtures from molecular simulation results of the mixture densities and Henry's law constants of the refrigerants in the DESs, coupled with phase equilibrium calculations and the enthalpies of the pure refrigerants. The largest efficiency was obtained for the mixture R245fa-ethaline (η = 6.82), followed by R245fa-levuline (η = 4.64) and HFO1336mzzE-levuline (η = 2.10). These modest efficiency values could be further increased by tailoring the cycle operating conditions to each particular refrigerant-DES system, as well as optimizing our choice of working fluid mixtures, neither of which we attempted in this study. Strong interactions were observed between the chlorine anions and some of the hydrogen atoms of the refrigerants, but in general the cation-refrigerant and HBD-refrigerant interactions are weaker compared to the refrigerant-refrigerant interactions. Refrigerant molecules have the largest diffusivities and make the cations, anions and HBD to move faster compared to systems of DESs without refrigerant; in general, species in refrigerant-ethaline mixtures have larger diffusivities compared to those for refrigerant-levuline mixtures. We also computed waste heat cycle efficiencies for the same R134a-DES mixtures studied in our previous work, finding significant differences between the efficiencies determined from molecular simulation data and those determined before using the COSMO-RS approach using two standard parametrizations. This observation suggests that further work is needed to improve the accuracy of the COSMO-RS predictions for these systems.

Computational Evaluation of Mixtures of Hydrofluorocarbons and Deep Eutectic Solvents for Absorption Refrigeration Systems.

We used computational tools to evaluate three working fluid mixtures for single-effect absorption refrigeration systems, where the generator (desorber) is powered by waste or solar heat. The mixtures studied here resulted from combining a widely used hydrofluorocarbon (HFC) refrigerant, R134a, with three common deep eutectic solvents (DESs) formed by mixing choline chloride (hydrogen bond acceptor, HBA) with urea, glycerol, or ethylene glycol as the hydrogen bond donor (HBD) species. The COSMOtherm/TmoleX software package was used in combination with refrigerant data from NIST/REFPROP, to perform a thermodynamic evaluation of absorption refrigeration cycles using the proposed working fluid mixtures. Afterward, classical MD simulations of the three mixtures were performed to gain insight on these systems at the molecular level. Larger cycle efficiencies are obtained when R134a is combined with choline chloride and ethylene glycol, followed by the system where glycerol is the HBD, and finally that where the HBD is urea. MD simulations indicate that the local density profiles of all species exhibit very sharp variations in systems containing glycerol or urea; furthermore, the Henry's law constants of R134a in these two systems are larger than those observed for the HFC in choline chloride and ethylene glycol, indicating that R134a is more soluble in the latter DES. Interaction energies indicate that the R134a-R134a interactions are weaker in the system where ethylene glycol is the HBD, as compared to in the other DES. Radial distribution functions confirm that in all systems, the DES species do not form strong directional interactions (e.g., hydrogen bonds) with the R134a molecules. Relatively strong interactions are observed between the Cl anions and the hydrogen atoms in R134a; however, the atom-atom interactions between R134a and the cation and HBD species are weaker and do not play a significant role in the solvation of the refrigerant. In all systems, R134a has the largest diffusion coefficients, followed by the HBD, the anion and the cation; the diffusion coefficients are the largest in the systems containing ethylene glycol, followed by those having glycerol and urea. This work is our first step toward our long-term goal of designing and demonstrating optimal working fluid mixtures for use in absorption refrigeration systems. Our results suggest that COSMO-RS can be used to perform a rapid screening of a large number of working fluid mixtures, and select a few candidates for further exploration using molecular simulations and experiments. These latter approaches can be used to refine the accuracy of the COSMO-RS predictions, and to optimize the selection of optimal working fluid mixtures for demonstration in absorption refrigeration systems powered by solar or waste heat sources.

Electrochemical Reduction of CO2 at Functionalized Au Electrodes.

Electrochemical reduction of CO2 provides an opportunity to store renewable energy as fuels with much greater energy densities than batteries. Product selectivity of the reduction reaction is known to be a function of the electrolyte and electrode; however, electrodes modified with functional ligands may offer new methods to control selectivity. Here, we report the electrochemical reduction of CO2 at functionalized Au surfaces with three thiol-tethered ligands: 2-mercaptopropionic acid, 4-pyridinylethanemercaptan, and cysteamine. Remarkably, Au electrodes modified with 4-pyridinylethanemercaptan show a 2-fold increase in Faradaic efficiency and 3-fold increase in formate production relative to Au foil. Conversely, electrodes with 2-mercaptopropionic acid ligands show nearly 100% Faradaic efficiency toward the hydrogen evolution reaction, while cystemine-modified electrodes show 2-fold increases in both CO and H2 production. We propose a proton-induced desorption mechanism associated with pKa of the functionalized ligand as responsible for the dramatic selectivity changes.

Low temperature preparation of crystalline ZrO2 coatings for improved elevated-temperature performances of Li-ion battery cathodes.

Ultrathin crystalline ZrO(2) nanofilms have been facilely deposited on LiMn(2)O(4) particles at 120 °C using atomic layer deposition. The ZrO(2) coating shows high crystallinity, conformality and homogeneity, which contribute to considerably improved electrochemical performance of LiMn(2)O(4) at elevated temperature in lithium-ion batteries.

Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.