Effect of glycerol concentration on rate and product speciation for Ni and Au-based catalysts.

In this paper, we investigate the glycerol electrooxidation reaction (GEOR) on Au and Ni catalysts, specifically the effect of glycerol concentration on electrochemical activity and product speciation for GEOR in an electrochemical flow cell system. With Au foil, cyclic voltammogram behavior shifted from hysteretic to near-linear by increasing the concentration of glycerol from 0.1 M to 1 M.

Identifying Reactive Trends in Glycerol Electro-Oxidation Using an Automated Screening Approach: 28 Ways to Electrodeposit an Au Electrocatalyst.

Automated, rapid electrocatalyst discovery techniques that comprehensively address the exploration of chemical spaces, characterization of catalyst robustness, reproducibility, and translation of results to (flow) electrolysis operation are needed. Responding to the growing interest in biomass valorization, we studied the glycerol electro-oxidation reaction (GEOR) on gold in alkaline media as a model reaction to demonstrate the efficacy of such methodology introduced here. Our platform combines individually addressable electrode arrays with HardPotato, a Python application programming interface for potentiostat control, to automate electrochemical experiments and data analysis operations.

Long-Range Surface Forces in Salt-in-Ionic Liquids.

Ionic liquids (ILs) are a promising class of electrolytes with a unique combination of properties, such as extremely low vapor pressures and nonflammability. Doping ILs with alkali metal salts creates an electrolyte that is of interest for battery technology. These salt-in-ionic liquids (SiILs) are a class of superconcentrated, strongly correlated, and asymmetric electrolytes.

Water in the Electrical Double Layer of Ionic Liquids on Graphene.

The performance of electrochemical devices using ionic liquids (ILs) as electrolytes can be impaired by water uptake. This work investigates the influence of water on the behavior of hydrophilic and hydrophobic ILs─with ethylsulfate and tris(perfluoroalkyl)trifluorophosphate or bis(trifluoromethyl sulfonyl)imide (TFSI) anions, respectively─on electrified graphene, a promising electrode material. The results show that water uptake slightly reduces the IL electrochemical stability and significantly influences graphene's potential of zero charge, which is justified by the extent of anion depletion from the surface.

Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes.

Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics.

Nanoheterogeneity of LiTFSI Solutions Transitions Close to a Surface and with Concentration.

Water-in-salt (WIS) electrolytes composed of 21 LiTFSI have recently emerged as a safe and environmentally friendly alternative to conventional organic electrolytes in Li-ion batteries. Several studies have emphasized the relation between the high conductivity of WIS electrolytes and their nanoscale structure. Combining force measurements with a surface forces apparatus and atomic force microscopy, this study describes the nanoheterogeneity of LiTFSI solutions as a function of concentration and distance from a negatively charged (mica) surface.

Effects of Superparamagnetic Iron Nanoparticles on Electrocatalysts for the Reduction of Oxygen.

It is of great research interest to understand the nanostructures contributing to the activity observed in the reduction of oxygen by non-platinum group metal (PGM) electrocatalysts in acidic media. Iron- and nitrogen-containing carbon networks are often the most studied structures, among which single-atom iron-coordinated nitrogen (FeN) moieties have often been proposed to be the structures leading to the high activity in these non-PGM electrocatalysts. Iron nanoparticles embedded within a carbon support are also formed under certain conditions as a result of the synthetic processes in making non-PGM electrocatalysts.

Oriented LiMnO Particle Fracture from Delithiation-Driven Surface Stress.

The insertion and removal of Li ions into Li-ion battery electrodes can lead to severe mechanical fatigue because of the repeated expansion and compression of the host lattice during electrochemical cycling. In particular, the lithium manganese oxide spinel (LiMnO, LMO) experiences a significant surface stress contribution to electrode chemomechanics upon delithiation that is asynchronous with the potentials where bulk phase transitions occur. In this work, we probe the stress evolution and resulting mechanical fracture from LMO delithation using an integrated approach consisting of cyclic voltammetry, electron microscopy, and density functional theory (DFT) calculations.

Covalent Ag-C Bonding Contacts from Unprotected Terminal Acetylenes for Molecular Junctions.

Robust molecule-metal linkages are essential for developing high-performance and air-stable devices for molecular and organic electronics. In this work, we report a facile method for forming robust and covalent bonding contacts between unprotected terminal acetylenes and metal (Ag) interfaces. Using this approach, we study the charge transport properties of conjugated oligophenylenes with covalent metal-carbon contacts to silver electrodes formed from unprotected terminal acetylene anchors.

Conversion of Co Nanoparticles to CoS in Metal-Organic Framework-Derived Porous Carbon during Cycling Facilitates NaS Reactivity in a Na-S Battery.

Room-temperature sodium-sulfur batteries have attracted wide interest due to their high energy density and high natural abundance. Polysulfide dissolution and irreversible NaS conversion are challenges to achieving high battery performance. Herein, we utilize a metal-organic framework-derived Co-containing nitrogen-doped porous carbon (CoNC) as a catalytic sulfur cathode host.

Preparation of Nonprecious Metal Electrocatalysts for the Reduction of Oxygen Using a Low-Temperature Sacrificial Metal.

Non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) are generally composed of iron, nitrogen, and carbon synthesized through high-temperature pyrolysis. Among the various types of precursors, metal-organic frameworks (MOFs), zeolitic imidazolate framework (ZIF)-8 in particular, have often been used in the synthesis. The pyrolysis of ZIF-8 precursor relies on the use of Zn as a sacrificial metal (SM), and the optimal processing temperatures often exceed 1000 °C to generate active non-PGM catalysts.

Chain length variation to probe the mechanism of accelerator additives in copper electrodeposition.

We evaluate the effect of chain length for a series of alkyl sulfonic acid additives on Cu electrodeposition by using a combination of electrochemical and Raman spectroscopic methods. Rotating disk linear sweep voltammetry revealed the influence of these additives on the bulk concentration of Cu+ and on the exchange current densities of the reduction of Cu2+/Cu+ and Cu+/Cu. We then used in situ shell-isolated, nanoparticle-enhanced Raman spectroscopy to correlate the additives' effects on deposition kinetics with their chemical structures at the electrode surface.

Understanding Ca Electrodeposition and Speciation Processes in Nonaqueous Electrolytes for Next-Generation Ca-Ion Batteries.

Electrochemical and analytical techniques were utilized to study Ca electrodeposition in nonaqueous electrolytes. Linear sweep voltammograms obtained at Au and Pt ultramicroelectrodes (UMEs) exhibit an inverse dependence between current density and scan rate, indicative of the presence of a chemical reaction step in a chemical-electrochemical (CE) deposition process. However, the magnitude of change in current density as a function of scan rate is larger at the Au UME than at the Pt UME.

Improving Cell Resistance and Cycle Life with Solvate-Coated Thiophosphate Solid Electrolytes in Lithium Batteries.

Solid electrolytes (SEs) have become a practical option for lithium ion and lithium metal batteries because of their improved safety over commercially available ionic liquids. The most promising of the SEs are the thiophosphates, whose excellent ionic conductivities at room temperature are comparable to those of commercially utilized ionic liquids. Hybrid solid-liquid electrolytes exhibit higher ionic conductivities than their bare SE counterparts because of decreased grain boundary resistance, enhanced interfacial contact with electrodes, and decreased degradation at the interface.

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10 S cm. With an experimentally measured activation barrier of 0.

Nanoporous Copper-Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO to Ethylene and Ethanol.

Electrodeposition of CuAg alloy films from plating baths containing 3,5-diamino-1,2,4-triazole (DAT) as an inhibitor yields high surface area catalysts for the active and selective electroreduction of CO to multicarbon hydrocarbons and oxygenates. EXAFS shows the co-deposited alloy film to be homogeneously mixed. The alloy film containing 6% Ag exhibits the best CO electroreduction performance, with the Faradaic efficiency for CH and CHOH production reaching nearly 60 and 25%, respectively, at a cathode potential of just -0.

Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems.

A comprehensive review of recent advances in the field of oxygen reduction electrocatalysis utilizing nonprecious metal (NPM) catalysts is presented. Progress in the synthesis and characterization of pyrolyzed catalysts, based primarily on the transition metals Fe and Co with sources of N and C, is summarized. Several synthetic strategies to improve the catalytic activity for the oxygen reduction reaction (ORR) are highlighted.

The Long-Term Stability of KO in K-O Batteries.

The rechargeable K-O battery is recognized as a promising energy storage solution owing to its large energy density, low overpotential, and high coulombic efficiency based on the single-electron redox chemistry of potassium superoxide. However, the reactivity and long-term stability of potassium superoxide remains ambiguous in K-O batteries. Parasitic reactions are explored and the use of ion chromatography to quantify trace amounts of side products is demonstrated.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li Solvation Structure and Li-S Battery Performance.

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI.

Gold Nanoparticles on Polymer-Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO.

Multiple approaches will be needed to reduce the atmospheric CO levels, which have been linked to the undesirable effects of global climate change. The electroreduction of CO driven by renewable energy is one approach to reduce CO emissions while producing chemical building blocks, but current electrocatalysts exhibit low activity and selectivity. Here, we report the structural and electrochemical characterization of a promising catalyst for the electroreduction of CO to CO: Au nanoparticles supported on polymer-wrapped multiwall carbon nanotubes.

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte.