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1.
Chem Mater ; 36(14): 7046-7055, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-39070673

RESUMO

Modern technologies that can replace state-of-the-art Li-ion batteries (LIBs), such as Na-ion batteries (NIBs), are currently driving new advancements in energy storage research. Developing functional active materials having sustainable features and enhanced performances able to assess their exploitation in the large-scale market represents a major challenge. Rationally designed P2-type layered transition metal (TM) oxides can enable high-energy NIB cathodes, where the tailored composition directly tunes the electrochemical and structural properties. Such positive electrodes need stable electrolytes, and exploration of unconventional room-temperature ionic liquid (RTIL)-based formulations paves the route toward safer options to flammable organic solvents. Notwithstanding the fact that Li+ doping in these materials has been proposed as a viable strategy to improve structural issues, an in-depth understanding of structure-property relationship as well as electrochemical testing with innovative RTIL-based electrolytes is still missing. Herein, we propose the solid-state synthesis of P2-Na0.84Li0.1Ni0.27Mn0.63O2 (NLNMO) cathode material, which exhibits promising structural reversibility and superior capacity retention upon cycling when tested in combination with RTIL-based electrolytes (EMI-, PYR14-, and N1114-FSI) compared to the standard NaClO4/PC. As unveiled from DFT calculations, lattice integrity is ensured by the reduced Jahn-Teller distortion upon Na removal exerted by Mn4+ and Li+ sublattices, while the good redox reversibility is mainly associated with the electrochemically active Ni2+/Ni3+/Ni4+ series burdening the charge compensation upon desodiation. By declaring the electrochemical compatibility of the P2-NLNMO cathode with three RTIL-based electrolytes and dissecting the role of Li/Ni/Mn sublattices in determining the electrochemical behavior, our comprehensive study enlightens the potential application of this electrode/electrolyte setup for future high-energy NIB prototype cells.

2.
Materials (Basel) ; 15(13)2022 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-35806750

RESUMO

Nanostructured cobalt oxide powders as electro catalysts for the oxygen evolution reaction (OER) in an alkaline membrane electrolysis cell (AME) were prepared by flame spray synthesis (FS); an AME's anode was then produced by depositing the FS prepared cobalt oxide powders on an AISI-316 sintered metal fiber by the electrophoretic deposition (EPD) method. FS powders and the composite electrode were characterized by SEM, XRD, and XPS analysis. The electrode showed an increase in the OER catalytic activity in a KOH 0.5 M solution with respect to commercial materials commonly applied in alkaline electrolysis, demonstrating that the flame spray synthesis of nanoparticles combined with the electrophoretic deposition technique represent an effective methodology for producing an anodic catalyst for alkaline membrane electrolyzers.

3.
Nat Mater ; 16(9): 925-931, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28714982

RESUMO

The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material's surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

4.
Chem Senses ; 38(5): 409-19, 2013 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-23599217

RESUMO

Chemosensory proteins (CSPs) are a class of small proteins expressed only in arthropods and endowed with heterogeneous functions. Some of them are involved in chemical communications, others in development or other physiological roles. The numbers of CSPs in different species of insects range from 4 in Drosophila to at least 70 in locusts, whereas in other arthropods such as crustaceans and millipedes, only 2-3 very similar sequences have been reported in each species. We have expressed, in a bacterial system, 5 of the 8 CSPs predicted by the genome of the malaria mosquito Anopheles gambiae, 4 identified at the protein level (SAP1, SAP2, SAP3, and CSP3) and a fifth annotated as part of this work, obtaining the proteins with high yields and in their soluble forms. Purified CSPs have been used to study their ligand-binding properties, both using competitive binding assays and quenching of intrinsic tryptophan fluorescence, in order to get insights into their physiological functions. The agreement between the 2 sets of data supports the assumptions that the ligands, including the fluorescent reporter, bind within the core of the proteins. Their different affinities toward a set of pure chemicals suggest specific roles in chemical communication.


Assuntos
Anopheles , Proteínas de Insetos/química , Proteínas de Insetos/metabolismo , Animais , Sítios de Ligação , Fluorescência , Proteínas de Insetos/isolamento & purificação , Ligantes , Triptofano/análise , Triptofano/química
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