A carbon supported platinum electrode in a bismuth saturated solution at a carefully chosen potential is capable of oxidizing glycerol to dihydroxyacetone with 100% selectivity. In the absence of bismuth, the primary alcohol oxidation is dominant. Using a combination of online HPLC and in situ FTIR, it is shown that Bi blocks the pathway for primary oxidation but also provides a specific Pt−Bi surface site poised for secondary alcohol oxidation.
The high polyphenol content of the wastewater is the major environmental problem caused by the olive mills. A pilot scale system for the treatment of the olive oil mills wastewater was developed aiming at the recovery of high added value-contained polyphenols and the reduction of the environmental problems. The treatment system consists of three main successive sections: The first one includes successive filtration stages aiming at the gradual reduction of the wastewater suspended solids up to a limit of 25 microm. The second section includes passing of the filtered wastewater through a series of adsorbent resins (XAD16 and XAD7HP) in order to achieve the de-odoring and decolorization of the wastewater and the removal/ recovery of the polyphenol and lactone content. The third section of the procedure includes the thermal evaporation and recovery of the organic solvents mixture, which has been used in the resin regeneration process, and finally the separation of the polyphenols and other organic substance contents using fast centrifuge partition chromatography. The final outcome of the whole procedure is (i) an odorless yellowish wastewater with a 99.99% reduced content in polyphenols and 98% reduced COD, (ii) an extract rich in polyphenols and lactones with high antioxidant activity and high added value, (iii) an extract containing the coloring substances of the olive fruit, and (iv) pure hydroxytyrosol.
We report a simple and effective electrochemical method to remove Fe impurities from commercial KOH electrolyte. We therefore utilize a MoS 2 catalyst deposited on porous Ni foam as both the anode and cathode in a two-electrode electrolysis setup. After 12 h of constant galvanostatic electrolysis at 100 mA, the Fe impurities from the KOH electrolyte were successfully removed, as confirmed by means of inductively coupled plasma optical emission spectroscopy analysis. In the purified KOH, a Ni−Co 3 O 4 composite oxide catalyst showed no Fe-induced activation. In contrast, we directly observed the uptake of Fe on the Ni−Co 3 O 4 catalyst from the nontreated electrolyte during catalyst operation using a coupled spectroelectrochemical setup. Interestingly, we further identified an influence on the dissolution behavior of Ni and Co in the presence of Fe impurities. Whereas hitherto mainly the activation effect of Fe impurities has been discussed, we hereby show that they additionally suppress corrosion under reaction conditions. Using our fast and low-cost method for the purification of large amounts of electrolyte, catalyst materials can be widely studied without these additional effects induced by Fe impurities in commercial KOH.
There is an ongoing debate on elucidating the actual role of Fe impurities in alkaline water electrolysis, acting either as reactivity mediators or as co-catalysts through synergistic interaction with the main catalyst material. This perspective summarizes the most prominent oxygen evolution reaction (OER) mechanisms mostly for Ni-based oxides as model transition metal catalysts and highlights the effect of Fe incorporation on the catalyst surface in the form of impurities originating from the electrolyte or co-precipitated in the catalyst lattice, in modulating the OER reaction kinetics, mechanism and stability.
Graphic Abstract
The oxygen evolution reaction (OER) is the limiting step in splitting water into its constituents, hydrogen and oxygen. Hence, research on potential OER catalysts has become the focus of many studies. In this work, we investigate capable OER catalysts but focus on catalyst stability, which is, especially in this case, at least equally as important as catalyst activity. We propose a specialized setup for monitoring the corrosion profiles of metal oxide catalysts during a stability testing protocol, which is specifically designed to standardize the investigation of OER catalysts by means of differentiating between catalyst corrosion and deactivation, oxygen evolution efficiency, and catalyst activity. For this purpose, we combined an electrochemical flow cell (EFC) with an oxygen sensor and an inductively coupled plasma–optical emission spectrometry (ICP-OES) system for the simultaneous investigation of catalyst deactivation, activity, and faradaic efficiency of catalysts. We tested various catalysts, with IrO2 and NiCoO2 used as benchmark materials in acidic and alkaline environment, respectively. The scalability of our setup will allow the user to investigate catalytic materials with supports of higher surface area than those which are typical for microelectrochemical flow cells (thus, under conditions more similar to those of commercial electrolyzers)
Exploiting the unique properties of three‐dimensional (3D) auxetic scaffolds in tissue engineering and regenerative medicine applications provides new impetus to these fields. Herein, the results on the fabrication and characterization of 3D auxetic scaffolds for tissue engineering applications are presented. The scaffolds are based on the well‐known re‐entrant hexagonal geometry (bowtie) and they are fabricated by multiphoton lithography using the organic−inorganic photopolymer SZ2080. In situ scanning electron microscopy–microindentations and nanoindention experiments are employed to characterize the photocurable resin SZ2080 and the scaffolds fabricated with it. Despite SZ2080 being a stiff material with a positive Poisson’s ratio, the scaffolds exhibit a negative Poisson’s ratio and high elasticity due to their architecture. Next, mouse fibroblasts are used to seed the scaffolds, showing that they can readily penetrate them and proliferate in them, adapting the scaffold shape to suit the cells’ requirements. Moreover, the scaffold architecture provides the cells with a predilection to specific directions, an imperative parameter for regenerative medicine in many cell‐based applications. This research paves the way for the utility of 3D auxetic metamaterials as the next‐generation adaptable scaffolds for tissue engineering.
Spinel-type
catalysts
are promising anode materials for the alkaline
oxygen evolution reaction (OER), exhibiting low overpotentials and
providing long-term stability. In this study, we compared two structurally
equal Co2FeO4 spinels with nominally identical
stoichiometry and substantially different OER activities. In particular,
one of the samples, characterized by a metastable precatalyst state,
was found to quickly achieve its steady-state optimum operation, while
the other, which was initially closer to the ideal crystallographic
spinel structure, never reached such a state and required 168 mV higher
potential to achieve 1 mA/cm2. In addition, the enhanced
OER activity was accompanied by a larger resistance to corrosion.
More specifically, using various ex situ, quasi in situ, and operando methods, we
could identify a correlation between the catalytic activity and compositional
inhomogeneities resulting in an X-ray amorphous Co2+-rich
minority phase linking the crystalline spinel domains in the as-prepared
state. Operando X-ray absorption spectroscopy revealed
that these Co2+-rich domains transform during OER to structurally
different Co3+-rich domains. These domains appear to be
crucial for enhancing OER kinetics while exhibiting distinctly different
redox properties. Our work emphasizes the necessity of the operando methodology to gain fundamental insight into the
activity-determining properties of OER catalysts and presents a promising
catalyst concept in which a stable, crystalline structure hosts the
disordered and active catalyst phase.
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