Role of Nanoscale Inhomogeneities in Co2FeO4 Catalysts during the Oxygen Evolution Reaction.

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.

3D Printing of Functional Metal and Dielectric Composite Meta-Atoms.

In this report, a novel fabrication method, based on casting Field's metal inside dielectric molds made via fused deposition modeling, is presented. Fused deposition modeling (FDM) has become one of the most common rapid prototyping methods. Whilst it generally produces good quality mechanical structures in thermoplastics, few reliable methods have been demonstrated that produce good quality 3D electrically conductive structures. By using Field's metal to transform dielectric molds into conductive structures, nearly any continuous metal geometry buried within the polymer can be created, allowing for the realization of complex 3D architectures. A wide range of thermoplastic materials used in fused deposition modeling have been investigated, to identify the best candidates in terms of processing temperature, relative permittivity, and loss tangent. Experimental measurements and X-ray computer tomography scans are used to determine the quality of structures fabricated using this method. Based on these findings, functional metamaterials devices operating at 600-700 MHz with high Q-factors have been produced. This method shows potential to be incorporated into standard FDM setups and could be utilized for the fabrication of curved and 3D geometries.

Electrochemical evaluation of the de-/re-activation of oxygen evolving Ir oxide.

Understanding the influence of dynamic and stationary polarization on the deactivation of state-of-the-art IrOx catalysts is imperative for the design and operation of robust and efficient proton exchange membrane water electrolyzers. In this work, the deactivation and activity regeneration of a commercial IrOx catalyst were investigated under potentiodynamic and potentiostatic conditions in acidic media using rotating disk electrode and electrogravimetry methods. Systematic electrochemical protocols were designed to decouple reversible from irreversible activity losses. Cyclic voltammetry provided a metric of the active surface area and traced the charge growth under different oxygen evolution reaction conditions. A direct log t dependent charge growth is observed, accompanied by the same fractional kinetic activity decay under potentiodynamic conditions. The loss is essentially recoverable after electrochemical reductive treatment, however at the expense of mild material dissolution. In contrast, an extended potentiostatic operation induced irreversible intrinsic degradation after a critical time (0.5-1 h), accompanied by stability enhancement. This irreversible deactivation is attributed to a gradual transformation of the hydrated IrOx to a dehydrated condensed oxide. Our results suggest that Ir dissolution during the regenerative treatment is not prohibitive, as long as the low potential modulations are not frequent.

Durable Nickel-Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts through Surface Functionalization with Tetraphenylporphyrin.

NiFe-based oxides are one of the best-known active oxygen evolution electrocatalysts. Unfortunately, they rapidly lost performance in Fe-purified KOH during the reaction. Herein, tetraphenylporphyrin (TPP) was loaded on a catalyst/electrolyte interface to alleviate the destabilization of NiFe (oxy)hydroxide. We propose that the degradation occurs primarily due to the release of thermodynamically unstable Fe. TPP acts as a protective layer and suppresses the dissolution of hydrated metal at the catalyst/electrolyte interface. In the electric double layer, the nonpolar TPP layer on the NiFe surface also invigorates the redeposition of the active site, Fe, which leads to prolonging the lifetime of NiFe. The TPP-coated NiFe was demonstrated in anion exchange membrane water electrolysis, where hydrogen was generated at a rate of 126 L h-1 for 115 h at a 1.41 mV h-1 degradation rate. Consequently, TPP is a promising protective layer that could stabilize oxygen evolution electrocatalysts.

Al2 Pt for Oxygen Evolution in Water Splitting: A Strategy for Creating Multifunctionality in Electrocatalysis.

The production of hydrogen via water electrolysis is feasible only if effective and stable catalysts for the oxygen evolution reaction (OER) are available. Intermetallic compounds with well-defined crystal and electronic structures as well as particular chemical bonding features are suggested here to act as precursors for new composite materials with attractive catalytic properties. Al2 Pt combines a characteristic inorganic crystal structure (anti-fluorite type) and a strongly polar chemical bonding with the advantage of elemental platinum in terms of stability against dissolution under OER conditions. We describe here the unforeseen performance of a surface nanocomposite architecture resulting from the self-organized transformation of the bulk intermetallic precursor Al2 Pt in OER.

Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability.

Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Pt(x)Co(1-x) colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal composition affects their electrocatalytic performance. The results show that upon contact with acid environment the Co leaches out of the particles leading to almost identical compositions, independent of the initial differences. Surprisingly the data show a clear trend in ORR activity, although the Pt(x)Co(1-x) nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process.

Ni-Xides (B, S, and P) for Alkaline OER: Shedding Light on Reconstruction Processes and Interplay with Incidental Fe Impurities as Synergistic Activity Drivers.

Ni-Xides (X = B, P, or S) exhibit intriguing properties that have endeared them for electrocatalytic water splitting. However, the role of B, P, and S, among others, in tailoring the catalytic performance of the Ni-Xides remains vaguely understood, especially if they are studied in unpurified KOH (Un-KOH) because of the renowned impact of incidental Fe impurities. Therefore, decoupling the effect induced by Fe impurities from inherent material reconstruction processes necessitates investigation of the materials in purified KOH solutions (P-KOH). Herein, studies of the OER on Ni2B, Ni2P, and Ni3S2 in P-KOH and Un-KOH coupled with in situ Raman spectroscopy, ex situ post-electrocatalysis, and online dissolution studies by ICP-OES are used to unveil the distinctive role of Ni-Xide reconstruction and the role of Fe impurities and their interplay on the electrocatalytic behavior of the three Ni-Xide precatalysts during the OER. There was essentially no difference in the OER activity and the electrochemical Ni2+/Ni3+ redox activation fingerprints of the three precatalysts via cyclic voltammetry in P-KOH, whereas their OER activity was considerably higher in Un-KOH with marked differences in the intrinsic activity and evolution of the Ni2+/Ni3+ fingerprint redox peaks. Thus, in the absence of Fe in the electrolyte (P-KOH), neither the nature of the guest element (B, P, and S) nor the underlying reconstruction processes are decisive activity drivers. This underscores the crucial role played by incidental Fe impurities on the OER activity of Ni-Xide precatalysts, which until now has been overlooked. In situ Raman spectroscopy revealed that the nickel hydroxide derived from Ni2B exhibits higher disorder than in the case of Ni2P and Ni3S2, both exhibiting a similar degree of disorder. The guest elements thus influence the degree of disorder of the formed nickel oxyhydroxides, which through their synergistic interaction with incidental Fe impurities concertedly realize high OER performance.

Tailoring the dispersion characteristics in planar arrays of discrete and coalesced split ring resonators.

In this report, the coupling and dispersion characteristics of discrete and coalesced square resonators was investigated in the MHz regime. Resonators with one and three gaps were considered. When the resonators are not in direct contact, the number of gaps has little effect upon the total coupling, which is negative. When the resonators are connected so that they share one side, the coupling can change drastically depending on the number of gaps. In particular, when the shared side has a gap, the total coupling coefficient switches to positive values, making it possible for forward travelling waves to propagate on arrays. Experimental, numerical and analytical data verify this behaviour.

Al-Pt compounds catalyzing the oxygen evolution reaction.

Al-Pt compounds have been systematically studied as electrocatalysts for the oxygen evolution reaction (OER). Considering the harsh oxidative conditions of the OER, all Al-Pt compounds undergo modifications during electrochemical experiments. However, the degree of changes strongly depends on the composition and crystal structure of a compound. In contrast to Al-rich compounds (Al4Pt and Al21Pt8), which reveal strong leaching of aluminum, changes in other compounds (Al2Pt, Al3Pt2, rt-AlPt, Al3Pt5, and rt-AlPt3) take place only on the surface or in the near-surface region. Furthermore, surface modification leads to a change in the electronic structure of Pt, giving rise to the in situ formation of catalytically more active surfaces, which are composed of intermetallic compounds, Pt-rich AlxPt1-x phases and Pt oxides. Forming a compromise between sufficient OER activity and stability, Al2Pt and Al3Pt2 can be considered as precursors for OER electrocatalysts.

Diffuse Tenosynovial Giant Cell Tumor Encircling the First Metatarsal Bone Remodeling after Resection. A Case Report.

Introduction: The term tenosynovial giant cell tumor encompasses a group of rare soft-tissue tumors. A new classification divides the group in localized and diffuse type, depending on the involvement of the surrounding tissues. Due to the unclear origin and heterogeneity in extend of the diffuse-type giant cell tumors, there is only limited evidence on the tumor-specific treatment. Thus, every case report has an added value toward setting disease-specific guidelines. Case Report: Presentation of a diffuse type tenosynovial giant cell tumor encircling the first metatarsal. The tumor had mechanically eroded the plantar aspect of the distal metaphysis, with no signs of tumor spread. After an open biopsy, resection of the mass was performed without debriding or resecting the first metatarsal. Repeat imaging postoperatively showed no recurrence at 4-year follow-up and a bony remodeling of the lesion. Conclusion: Bone remodeling is possible after complete resection of diffuse tenosynovial giant cell tumor when the erosion is caused by mechanical pressure and no intraosseous expansion of the tumor is present.

Design and Characterization of Microscale Auxetic and Anisotropic Structures Fabricated by Multiphoton Lithography.

The need for control of the elastic properties of architected materials has been accentuated due to the advances in modelling and characterization. Among the plethora of unconventional mechanical responses, controlled anisotropy and auxeticity have been promulgated as a new avenue in bioengineering applications. This paper aims to delineate the mechanical performance of characteristic auxetic and anisotropic designs fabricated by multiphoton lithography. Through finite element analysis the distinct responses of representative topologies are conveyed. In addition, nanoindentation experiments observed in-situ through scanning electron microscopy enable the validation of the modeling and the observation of the anisotropic or auxetic phenomena. Our results herald how these categories of architected materials can be investigated at the microscale.

Tuning of Reciprocal Carbon-Electrode Properties for an Optimized Hydrogen Evolution.

Closing the material cycle for harmful and rare resources is a key criterion for sustainable and green energy systems. The concept of using scalable biomass-derived carbon electrodes to produce hydrogen from water was proposed here, satisfying the need for sustainability in the field of chemical energy conversion. The carbon electrodes exhibited not only water oxidation activity but also a strong self-oxidation when being used as anode for water splitting. The carbon oxidation, which is more energy-favorable, was intentionally allowed to occur for an improvement of the total current, thus enhancing the hydrogen production on the cathode side. By introducing different earth-abundant metals, the electrode could be well adjusted to achieve an optimized water/carbon oxidation ratio and an appreciable reactivity for practical applications. This promising methodology may become a very large driver for carbon chemistry when waste organic materials or biomass can be converted using its intrinsic energy content of carbon. Such a process could open a safe path for sub-zero CO2 emission control. The concept of how and which parameter of a carbon-based electrode can be optimized was presented and discussed in this paper.

A new process for the management of olive oil mill waste water and recovery of natural antioxidants.

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.

Spontaneously Healed Pathologic Fracture over a Critical-Size Calcaneal Cyst.

Simple bone cysts are nonsymptomatic lesions. They typically involve the medullary cavity, but they can also be found in nonlong bones such as the calcaneum. Their treatment remains controversial varying from observation and conservative healing to irritating injections or bone grafting. In the case of a pathologic fracture, surgical treatment seems most appropriate especially when the cyst is situated on a weight-bearing bone. We present herein the rare case of a spontaneously healed pathological fracture over a critical-size calcaneal cyst of a patient reluctant to undergo surgical treatment. An interpretation of the healing procedure as well as a review of the literature is presented.