RESUMEN

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

RESUMEN

Optimized catalytic properties and reactant adsorption energy played a crucial role in promoting CO2 electrocatalysis. Herein, Cu7S4/Cu underwent in situ dynamic restructuring to generate S-Cu2O/Cu hybrid catalyst for effective electrochemical CO2 reduction to formate that outperformed Cu2O/Cu and Cu7S4. Thermodynamic and in situ Raman spectra revealed that the optimized adsorption of the HCOO* intermediate on S-Cu2O/Cu was regulated and the H2 pathway (surface H) was suppressed by S-doping. Meanwhile, Cu7S4/Cu nanoflowers created abundant boundaries for ECR and strengthened the CO2 adsorption by inducing Cu. These findings provide a new perspective on synthetic methods for various electrocatalytic reduction processes.

RESUMEN

The increasing global demand for sustainable energy sources and emerging environmental issues have pushed the development of energy conversion and storage technologies to the forefront of chemical research. Electrochemical carbon dioxide (CO2 ) conversion provides an attractive approach to synthesizing fuels and chemical feedstocks using renewable energy. On the path to deploying this technology, basic and applied scientific hurdles remain. Copper, as the only metal catalyst that is capable to produce C2+ fuels from CO2 reduction (CO2 R), still faces challenges in the improvement of electrosynthesis pathways for highly selective fuel production. In this regard, mechanistically understanding CO2 R on Cu-based electrocatalysts, particularly identifying the structure-function correlation, is crucial. Here, a broad view of the variable structural parameters and their complex interplay in CO2 R catalysis on Cu was given, with the purpose of providing deep insights and guiding the future rational design of CO2 R electrocatalysts. First, this Review described the progress and recent advances in the development of well-defined nanostructured catalysts and the mechanistic understanding on the influences from a particular structure of a catalyst, such as facet, defects, morphology, oxidation state, composition, and interface. Next, the in-situ dynamic restructuring of Cu was presented. The importance of operando characterization methods to understand the catalyst structure-sensitivity was also discussed. Finally, some perspectives on the future outlook for electrochemical CO2 R were offered.

RESUMEN

With ever-increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO2 RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S-doping and Cu-alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2 RR.

RESUMEN

BACKGROUND: Gummy smile (GS) is a nonpathological condition causing esthetic disharmony in which an excessive amount of gingival tissue is exposed when smiling. Nowadays, there is not unanimous agreement regarding both classification and management of GS. This study aimed to present an organized and comprehensive clinical classification of the GS, as well as to discuss a therapeutic approach, with hyaluronic acid dermal fillers. METHODS: This study is presenting the clinical experience of the authors regarding GS. RESULTS: The Mercado-Rosso GS classification has into account aesthetic aspects, etiopathogenetic criteria, and functional aspects of the smile. According to Mercado-Rosso GS-classification-system, GS is divided into 3-types: Type 1, characterized by a lack of support and/or a lack of projection of the upper maxilla; Type 2, due to an imbalance between the strength (excess) and the resistance (defect) of the levator muscles; and Type 3, defined by an excessive strength of the zygomatic muscles, which causes a wide smile and an excessive visualization of the molar teeth. CONCLUSIONS: The Mercado-Rosso GS classification system is a tool that facilitates the diagnostic and therapeutic approach to the gummy smile. RD Dynamic Restructuring® constitutes a comprehensive therapeutic approach that makes reference to both the effect of the HA filler on the muscle movement and the balance between the muscle strength and the resistance of the soft tissue to be folded in different facial structures). LEVEL OF EVIDENCE: Level V.

Asunto(s)

RESUMEN

A linear spectral mapping technique was applied to monitor the growth of biomolecular absorption bands at the bio-interface of a nascent Pseudomonas fluorescens biofilm during and after interaction with a surface-adhered air bubble. Attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectra were obtained in different locations in a microchannel with adequate spatial and temporal resolution to study the effect of a static bubble on the evolution of protein and lipid signals at the ATR crystal surface. The results reveal that the presence of a bubble during the lag phase modified levels of extracellular lipids and affected a surface restructuring process, many hours after the bubble's disappearance.

Asunto(s)