Tailoring Cu Electrodes for Enhanced CO2 Electroreduction through Plasma Electrolysis in Non-Conventional Phosphorus-Oxoanion-Based Electrolytes.

This study presents a green, ultra-fast, and facile technique for the fabrication of micro/nano-structured and porous Cu electrodes through in-liquid plasma electrolysis using phosphorous-oxoanion-based electrolytes. Besides the preferential surface faceting, the Cu electrodes exhibit unique surface structures, including octahedral nanocrystals besides nanoporous and microporous structures, depending on the employed electrolyte. The incorporation of P-atoms into the Cu surfaces is observed. The modified Cu electrodes display increased roughness, leading to higher current densities for CO2 electroreduction reaction. The selectivity of the modified Cu electrodes towards C2 products is highest for the Cu electrodes treated in Na2 HPO3 and Na3 PO4 electrolytes, whereas those treated in Na2 H2 PO2 produce the most H2 . The Cu electrode treated in Na3 PO4 produces ethylene (23 %) at -1.1 V vs. RHE, and a comparable amount of acetaldehyde (15 %) that is typically observed for Cu(110) single crystals. The enhanced selectivity is attributed to several factors, including the surface morphology, the incorporation of phosphorus into the Cu structure, and the formation of Cu(110) facets. Our results not only advance our understanding of the influence of the electrolyte's nature on the plasma electrolysis of Cu electrodes, but also underscores the potential of in-liquid plasma treatment for developing efficient Cu electrocatalysts for sustainable CO2 conversion.

In-Liquid Plasma-Mediated Manganese Oxide Electrocatalysts for Quasi-Industrial Water Oxidation and Selective Dehydrogenation.

The production of renewable feedstocks through the coupled oxygen evolution reaction (OER) with selective organic oxidation requires a perfect balance in the choice of a catalyst and its synthesis access, morphology, and catalytic activity. Herein we report a rapid in-liquid plasma approach to produce a hierarchical amorphous birnessite-type manganese oxide layer on 3D nickel foam. The as-prepared anode exhibits an OER activity with overpotentials of 220, 250, and 270 mV for 100, 500, and 1000 mA·cm-2, respectively, and can spontaneously be paired with chemoselective dehydrogenation of benzylamine under both ambient and industrial (6 M KOH, 65 °C) alkaline conditions. The in-depth ex-situ and in-situ characterization unequivocally demonstrate the intercalation of potassium in the birnessite-type phase with prevalent MnIII states as an active structure, which displays a trade-off between porous morphology and bulk volume catalytic activity. Further, a structure-activity relationship is realized based on the cation size and structurally similar manganese oxide polymorphs. The presented method is a substantial step forward in developing a robust MnOx catalyst for combining effective industrial OER and value-added organic oxidation.

Structural Evolution of Pt, Au and Cu Anodes by Electrolysis up to Contact Glow Discharge Electrolysis in Alkaline Electrolytes*.

Applying a voltage to metal electrodes in contact with aqueous electrolytes results in the electrolysis of water at voltages above the decomposition voltage and plasma formation in the electrolyte at much higher voltages referred to as contact glow discharge electrolysis (CGDE). While several studies explore parameters that lead to changes in the I-U characteristics in this voltage range, little is known about the evolution of the structural properties of the electrodes. Here we study this aspect on materials essential to electrocatalysis, namely Pt, Au, and Cu. The stationary I-U characteristics are almost identical for all electrodes. Detailed structural characterization by optical microscopy, scanning electron microscopy, and electrochemical approaches reveal that Pt is stable during electrolysis and CGDE, while Au and Cu exhibit a voltage-dependent oxide formation. More importantly, oxides are reduced when the Au and Cu electrodes are kept in the electrolysis solution after electrolysis. We suspect that H2 O2 (formed during electrolysis) is responsible for the oxide reduction. The reduced oxides (which are also accessible via electrochemical reduction) form a porous film, representing a possible new class of materials in energy storage and conversion studies.

Plasma Electrolytic Oxidation (PEO) Process-Processing, Properties, and Applications.

Plasma electrolytic oxidation (PEO) is a novel surface treatment process to produce thick, dense metal oxide coatings, especially on light metals, primarily to improve their wear and corrosion resistance. The coating manufactured from the PEO process is relatively superior to normal anodic oxidation. It is widely employed in the fields of mechanical, petrochemical, and biomedical industries, to name a few. Several investigations have been carried out to study the coating performance developed through the PEO process in the past. This review attempts to summarize and explain some of the fundamental aspects of the PEO process, mechanism of coating formation, the processing conditions that impact the process, the main characteristics of the process, the microstructures evolved in the coating, the mechanical and tribological properties of the coating, and the influence of environmental conditions on the coating process. Recently, the PEO process has also been employed to produce nanocomposite coatings by incorporating nanoparticles in the electrolyte. This review also narrates some of the recent developments in the field of nanocomposite coatings with examples and their applications. Additionally, some of the applications of the PEO coatings have been demonstrated. Moreover, the significance of the PEO process, its current trends, and its scope of future work are highlighted.

Facile Access to an Active γ-NiOOH Electrocatalyst for Durable Water Oxidation Derived From an Intermetallic Nickel Germanide Precursor.

Identifying novel classes of precatalysts for the oxygen evolution reaction (OER by water oxidation) with enhanced catalytic activity and stability is a key strategy to enable chemical energy conversion. The vast chemical space of intermetallic phases offers plenty of opportunities to discover OER electrocatalysts with improved performance. Herein we report intermetallic nickel germanide (NiGe) acting as a superior activity and durable Ni-based electro(pre)catalyst for OER. It is produced from a molecular bis(germylene)-Ni precursor. The ultra-small NiGe nanocrystals deposited on both nickel foam and fluorinated tin oxide (FTO) electrodes showed lower overpotentials and a durability of over three weeks (505 h) in comparison to the state-of-the-art Ni-, Co-, Fe-, and benchmark NiFe-based electrocatalysts under identical alkaline OER conditions. In contrast to other Ni-based intermetallic precatalysts under alkaline OER conditions, an unexpected electroconversion of NiGe into γ-NiIII OOH with intercalated OH- /CO3 2- transpired that served as a highly active structure as shown by various ex situ methods and quasi in situ Raman spectroscopy.

Ion transport in a polymer-plastic solid soft matter electrolyte in the light of solvent dynamics and ion association.

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state, compliable mechanical strength (approximately 1 MPa), and wide electrochemical voltage stability (> or = 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO(4))-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO(4)-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polymer concentration shows an effective increase in trans conformer concentration along with free Li(+) ion concentration. This strongly supports the view that enhancement in LiClO(4)-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO(4)-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO(4)-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance (1)H and (7)Li line width measurements.

Study of ion transport in lithium perchlorate-succinonitrile plastic crystalline electrolyte via ionic conductivity and in situ cryo-crystallography.

Ion transport mechanism in lithium perchlorate (LiClO(4))-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO(4)-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO(4)-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.