Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces.

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. This study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.

Total Electrosynthesis of N, N-Dimethylformamide From CO and NO.

Electrochemical C-N coupling presents a promising strategy for converting abundant small molecules like CO and NO to produce low-carbon-intensity chemicals in a potentially more sustainable route. A prominent challenge is the limited product scope, particularly for organonitrogen chemicals featuring a variety of functional groups, alongside the limited understanding of plausible reaction mechanisms leading up to these products. In light of this, the total electrosynthesis method is reported for producing N, N-dimethylformamide (DMF), a widespread solvent and commodity chemical, from NO and CO.

Hydrophobic assembly of molecular catalysts at the gas-liquid-solid interface drives highly selective CO electromethanation.

Molecular catalysts offer tunable active and peripheral sites, rendering them ideal model systems to explore fundamental concepts in catalysis. However, hydrophobic designs are often regarded as detrimental for dissolution in aqueous electrolytes. Here we show that established cobalt terpyridine catalysts modified with hydrophobic perfluorinated alkyl side chains can assemble at the gas-liquid-solid interfaces on a gas diffusion electrode.

Terpyridine-Decorated Polymer Nanosphere Latex: Template Nanocarriers for the Synthesis of Cu-CeO Hollow Spheres.

Water-soluble polymers with the ability to complex metal ions through complexing ligands have attracted significant interest in diverse domains, such as optical or catalyst applications. In this paper, we successfully synthesized, through a one-pot process combining polymerization-induced self-assembly and reversible addition-fragmentation chain transfer polymerization, aqueous dispersions of terpyridine-decorated poly[poly(ethylene glycol)methyl ether methacrylate]--poly(methyl methacrylate) (tpy-PPEGMA--PMMA) amphiphilic block copolymers. The formation of well-defined amphiphilic block copolymers and their self-assembly led to nanosphere latex with the hydrodynamic diameters increasing from 17 to 52 nm and the length of the copolymers increasing from 21,000 to 51,000 g·mol.

Butyric acid and prospects for creation of new medicines based on its derivatives: a literature review.

The widespread use of antimicrobials causes antibiotic resistance in bacteria. The use of butyric acid and its derivatives is an alternative tactic. This review summarizes the literature on the role of butyric acid in the body and provides further prospects for the clinical use of its derivatives and delivery methods to the animal body.

Combined electrochemical and spectroscopic investigations of carbonate-mediated water oxidation to peroxide.

The development of electrosynthetic technologies for HO production is appealing from a sustainability perspective. The use of carbonate species as mediators in water oxidation to peroxide has emerged as a viable route to do so but still many questions remain about the mechanism that must be addressed. To this end, this work combines electrochemical and spectroscopic methods to investigate reaction pathways and factors influencing the efficiency of this reaction.

Electrocatalysis with molecules and molecular assemblies within gas diffusion electrodes.

Molecular catalysts and their assemblies are important model systems in electrocatalysis. This is largely because their active sites, secondary coordination spheres, and reaction environments can be rationally modulated. Such experiments yield important insights into the structure-activity relationships that can be used to design improved catalysts or translated to more technologically mature systems.

Construction of C-N bonds from small-molecule precursors through heterogeneous electrocatalysis.

Energy-intensive thermochemical processes within chemical manufacturing are a major contributor to global CO emissions. With the increasing push for sustainability, the scientific community is striving to develop renewable energy-powered electrochemical technologies in lieu of CO-emitting fossil-fuel-driven methods. However, to fully electrify chemical manufacturing, it is imperative to expand the scope of electrosynthetic technologies, particularly through the innovation of reactions involving nitrogen-based reactants.

Electrochemically driven C-N bond formation from CO and ammonia at the triple-phase boundary.

Electrosynthetic techniques are gaining prominence across the fields of chemistry, engineering and energy science. However, most works within the direction of synthetic heterogeneous electrocatalysis focus on water electrolysis and CO reduction. In this work, we moved to expand the scope of small molecule electrosynthesis by developing a synthetic scheme which couples CO and NH at a gas-liquid-solid boundary to produce species with C-N bonds.

Pushing the methodological envelope in understanding the photo/electrosynthetic materials-microorganism interface.

Biohybrid photo/electrosynthetic systems synergize microbial metabolic pathways and inorganic materials to generate the fuels and chemicals to power our society. They aim to combine the strengths of product selectivity from biological cells and efficient charge generation and light absorption of inorganic materials. However crucial mechanistic questions still remain.

Conductive Metal-Organic Frameworks Bearing M-O Active Sites as Highly Active Biomass Valorization Electrocatalysts.

The electrochemical oxidation of the biomass platform 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), is an important reaction in the emerging area of renewable energy-powered biomass valorization. A key limitation in this field is the ill-defined nature of the catalytic sites of the highest-performing materials that limits the fundamental insights that can be extracted. To this end, a conductive metal-organic framework-based electrocatalytic model system with well-defined M-O active sites for electrochemical HMF oxidation was developed.

Rational incorporation of defects within metal-organic frameworks generates highly active electrocatalytic sites.

The allure of metal-organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid.

Applicability of modified carbon sorbent for removing potentially toxic biologically active molecules of aromatic structure from blood plasma.

The modification of the mesoporous carbon sorbent with 3-phenylpropanoic acid was carried out in order to create preparations of complex, prolonged action, exhibiting detoxifying, antibacterial, and antifungal properties due to the applied modifier, which is capable of migrating into the solution and exhibiting its own biospecific properties. A technique was developed for fixing 3-phenylpropionic acid (PhPA) on a carbon support by its adsorption from solution. Three types of sorbents with various content of the modifier (PhPA) and the sorbent without modifier were studied.

Probing electrosynthetic reactions with furfural on copper surfaces.

This work entails the integrated use of electrochemistry and operando Raman spectroscopy to probe the reduction of a biomass platform, furfural, to value-added chemicals on Cu electrodes. The results reveal key structural differences of the Cu that dictate selectivity for furfuryl alcohol or 2-methylfuran.

Towards atomic precision in HMF and methane oxidation electrocatalysts.

With the increasing emphasis on transitioning to a sustainable society, electrosynthetic routes to generate fuels and chemicals are rapidly gaining traction. While the electrolysis of water and CO2 has been heavily investigated over the last decade, electrocatalysis of other abundant resources such as biomass and methane is now increasingly coming into focus. As this area is relatively less mature, much work remains to be done.

Anti-inflammatory and antidiabetic effects of grape-derived stilbene concentrate in the experimental metabolic syndrome.

Aims: This study aimed to investigate the carbohydrate and lipid dynamics, associated inflammation markers and the effectiveness of a grape-derived stilbene concentrate (GDSC) treatment in experimental metabolic syndrome (MetS).

Methods: The study was carried out on 40 male 12-weeks of age Wistar rats. The MetS was induced using the fructose model (feeding with 60%-solid fructose diet for 24 weeks).

spectroscopy of nanoscopic metal/covalent organic framework electrocatalysts.

Metal and covalent organic frameworks (MOFs and COFs) are increasingly finding exceptional utility in electrocatalytic systems. Their chemically defined porous nature grants them key functions that may enhance their electrocatalytic performance relative to conventional molecular or heterogeneous materials. In order to obtain insights into their function, mechanism, and dynamics under electrocatalytic conditions, operando spectroscopy, that which is performed as the catalyst is functioning, has been increasingly applied.

Speeding up Nanoscience and Nanotechnology with Ultrafast Plasmonics.

Surface plasmons are collective oscillations of free electrons at the interface between a conducting material and the dielectric environment. These excitations support the formation of strongly enhanced and confined electromagnetic fields. As well, they display fast dynamics lasting tens of femtoseconds and can lead to a strong nonlinear optical response at the nanoscale.

Mechanochemical synthesis of cobalt/copper fluorophosphate generates a multifunctional electrocatalyst.

The utilisation of inductive effects is emerging as a powerful tool to enhance material properties. Within the context of electrocatalysis, such effects may alter an active site's electronic structure and consequently, its catalytic activity. To this end, we introduce catalytically active cobalt species within an electron-withdrawing copper fluorophosphate host via a mechanochemical synthetic method.

Electrochemically Triggered Dynamics within a Hybrid Metal-Organic Electrocatalyst.

A wide array of systems, ranging from enzymes to synthetic catalysts, exert adaptive motifs to maximize their functionality. In a related manner, select metal-organic frameworks (MOFs) and similar systems exhibit structural modulations under stimuli such as the infiltration of guest species. Probing their responsive behavior is a challenging but important step toward understanding their function and subsequently building functional systems.

Electrochemical biomass valorization on gold-metal oxide nanoscale heterojunctions enables investigation of both catalyst and reaction dynamics with surface-enhanced Raman spectroscopy.

The electrochemical oxidation of biomass platforms such as 5-hydroxymethylfurfural (HMF) to value-added chemicals is an emerging clean energy technology. However, mechanistic knowledge of this reaction in an electrochemical context is still lacking and studies are even more rare. In this work, we utilize core-shell gold-metal oxide nanostructures which enable surface-enhanced Raman spectroelectrochemical studies to simultaneously visualize catalyst material transformation and surface reaction intermediates under an applied voltage.

Disparity of Cytochrome Utilization in Anodic and Cathodic Extracellular Electron Transfer Pathways of Biofilms.

Extracellular electron transfer (EET) in microorganisms is prevalent in nature and has been utilized in functional bioelectrochemical systems. EET of has been extensively studied and has been revealed to be facilitated through -type cytochromes, which mediate charge between the electrode and in anodic mode. However, the EET pathway of cathodic conversion of fumarate to succinate is still under debate.

Investigation of mixed-metal (oxy)fluorides as a new class of water oxidation electrocatalysts.

The development of electrocatalysts for the oxygen evolution reaction (OER) is one of the principal challenges in the area of renewable energy research. Within this context, mixed-metal oxides have recently emerged as the highest performing OER catalysts. Their structural and compositional modification to further boost their activity is crucial to the wide-spread use of electrolysis technologies.