In Situ X-ray Absorption Spectroscopy of Metal/Nitrogen-doped Carbons in Oxygen Electrocatalysis

Metal/nitrogen-doped carbons (M−N−C) are promising candidates as oxygen electrocatalysts due to their low cost, tunable catalytic activity and selectivity, and well-dispersed morphologies. To improve the electrocatalytic performance of such systems, it is critical to gain a detailed understanding of their structure and properties through advanced characterization. In situ X-ray absorption spectroscopy (XAS) serves as a powerful tool to probe both the active sites and structural evolution of catalytic materials under reaction conditions. In this review, we firstly provide an overview of the fundamental concepts of XAS and then comprehensively review the setup and application of in situ XAS, introducing electrochemical XAS cells, experimental methods, as well as primary functions on catalytic applications. The active sites and the structural evolution of M−N−C catalysts caused by the interplay with electric fields, electrolytes and reactants/intermediates during the oxygen evolution reaction and the oxygen reduction reaction are subsequently discussed in detail. Finally, major challenges and future opportunities in this exciting field are highlighted.</p

Graphene-based metal-organic framework hybrids for applications in catalysis, environmental, and energy technologies

Current energy and environmental challenges demand the development and design of multifunctional porous materials with tunable properties for catalysis, water purification, and energy conversion and storage. Because of their amenability to de novo reticular chemistry, metal-organic frameworks (MOFs) have become key materials in this area. However, their usefulness is often limited by low chemical stability, conductivity and inappropriate pore sizes. Conductive two-dimensional (2D) materials with robust structural skeletons and/or functionalized surfaces can form stabilizing interactions with MOF components, enabling the fabrication of MOF nanocomposites with tunable pore characteristics. Graphene and its functional derivatives are the largest class of 2D materials and possess remarkable compositional versatility, structural diversity, and controllable surface chemistry. Here, we critically review current knowledge concerning the growth, structure, and properties of graphene derivatives, MOFs, and their graphene@MOF composites as well as the associated structure- property-performance relationships. Synthetic strategies for preparing graphene@MOF composites and tuning their properties are also comprehensively reviewed together with their applications in gas storage/separation, water purification, catalysis (organo-, electro-, and photocatalysis), and electrochemical energy storage and conversion. Current challenges in the development of graphene@MOF hybrids and their practical applications are addressed, revealing areas for future investigation. We hope that this review will inspire further exploration of new graphene@MOF hybrids for energy, electronic, biomedical, and photocatalysis applications as well as studies on previously unreported properties of known hybrids to reveal potential "diamonds in the rough".Web of Science12224173381724

Biotechnological production and application of fructooligosaccharides

Currently, prebiotics are all carbohydrates of relatively short chain length. An important group is the fructooligosaccharides, which are a special kind of prebiotics associated to their selective stimulation of the activity of certain groups of colonic bacteria that have a positive and beneficial effect on intestinal microbiota, reducing incidence of gastrointestinal infections, respiratory and also possessing a recognized bifidogenic effect. Traditionally, these prebiotic compounds have been obtained through extraction processes from some plants, as well as through enzymatic hydrolysis of sucrose. However, different fermentative methods have also been proposed for the production of fructooligosaccharides, such as solid-state fermentation utilizing various agroindustrial by-products. By optimizing the culture parameters, fructooligosaccharides yields and productivity can be improved. The use of immobilized enzymes and cells has also been proposed as being an effective and economic method for large-scale production of fructooligosaccharides. This paper is an overview on the results of recent studies on fructooligosacharides biosynthesis, physicochemical properties, sources, biotechnological production and applications.The authors thank the National Council of Science and Technology of Mexico (CONACYT) for funding this study. D. A. Flores-Maltos thank the CONACYT for the financial support provided for her postgraduate studies in the Food Science and Technology Program, Universidad Autonoma de Coahuila, Mexico

The evolution of the ventilatory ratio is a prognostic factor in mechanically ventilated COVID-19 ARDS patients

Background: Mortality due to COVID-19 is high, especially in patients requiring mechanical ventilation. The purpose of the study is to investigate associations between mortality and variables measured during the first three days of mechanical ventilation in patients with COVID-19 intubated at ICU admission. Methods: Multicenter, observational, cohort study includes consecutive patients with COVID-19 admitted to 44 Spanish ICUs between February 25 and July 31, 2020, who required intubation at ICU admission and mechanical ventilation for more than three days. We collected demographic and clinical data prior to admission; information about clinical evolution at days 1 and 3 of mechanical ventilation; and outcomes. Results: Of the 2,095 patients with COVID-19 admitted to the ICU, 1,118 (53.3%) were intubated at day 1 and remained under mechanical ventilation at day three. From days 1 to 3, PaO2/FiO2 increased from 115.6 [80.0-171.2] to 180.0 [135.4-227.9] mmHg and the ventilatory ratio from 1.73 [1.33-2.25] to 1.96 [1.61-2.40]. In-hospital mortality was 38.7%. A higher increase between ICU admission and day 3 in the ventilatory ratio (OR 1.04 [CI 1.01-1.07], p = 0.030) and creatinine levels (OR 1.05 [CI 1.01-1.09], p = 0.005) and a lower increase in platelet counts (OR 0.96 [CI 0.93-1.00], p = 0.037) were independently associated with a higher risk of death. No association between mortality and the PaO2/FiO2 variation was observed (OR 0.99 [CI 0.95 to 1.02], p = 0.47). Conclusions: Higher ventilatory ratio and its increase at day 3 is associated with mortality in patients with COVID-19 receiving mechanical ventilation at ICU admission. No association was found in the PaO2/FiO2 variation

Clustering COVID-19 ARDS patients through the first days of ICU admission. An analysis of the CIBERESUCICOVID Cohort

Background Acute respiratory distress syndrome (ARDS) can be classified into sub-phenotypes according to different inflammatory/clinical status. Prognostic enrichment was achieved by grouping patients into hypoinflammatory or hyperinflammatory sub-phenotypes, even though the time of analysis may change the classification according to treatment response or disease evolution. We aimed to evaluate when patients can be clustered in more than 1 group, and how they may change the clustering of patients using data of baseline or day 3, and the prognosis of patients according to their evolution by changing or not the cluster.Methods Multicenter, observational prospective, and retrospective study of patients admitted due to ARDS related to COVID-19 infection in Spain. Patients were grouped according to a clustering mixed-type data algorithm (k-prototypes) using continuous and categorical readily available variables at baseline and day 3.Results Of 6205 patients, 3743 (60%) were included in the study. According to silhouette analysis, patients were grouped in two clusters. At baseline, 1402 (37%) patients were included in cluster 1 and 2341(63%) in cluster 2. On day 3, 1557(42%) patients were included in cluster 1 and 2086 (57%) in cluster 2. The patients included in cluster 2 were older and more frequently hypertensive and had a higher prevalence of shock, organ dysfunction, inflammatory biomarkers, and worst respiratory indexes at both time points. The 90-day mortality was higher in cluster 2 at both clustering processes (43.8% [n = 1025] versus 27.3% [n = 383] at baseline, and 49% [n = 1023] versus 20.6% [n = 321] on day 3). Four hundred and fifty-eight (33%) patients clustered in the first group were clustered in the second group on day 3. In contrast, 638 (27%) patients clustered in the second group were clustered in the first group on day 3.Conclusions During the first days, patients can be clustered into two groups and the process of clustering patients may change as they continue to evolve. This means that despite a vast majority of patients remaining in the same cluster, a minority reaching 33% of patients analyzed may be re-categorized into different clusters based on their progress. Such changes can significantly impact their prognosis

Nafion-Induced Reduction of Manganese and Its Impact on the Electrocatalytic Properties of a Highly Active MnFeNi Oxide for Bifunctional Oxygen Conversion

Electrocatalysts for bifunctional oxygen reduction (ORR) and oxygen evolution reaction (OER) are commonly studied under hydrodynamic conditions, rendering the use of binders necessary to ensure the mechanical stability of the electrode films. The presence of a binder, however, may influence the properties of the materials under examination to an unknown extent. Herein, we investigate the impact of Nafion on a highly active ORR/OER catalyst consisting of MnFeNi oxide nanoparticles supported on multi-walled carbon nanotubes. Electrochemical studies revealed that, in addition to enhancing the mechanical stability and particle connectivity, Nafion poses a major impact on the ORR selectivity, which correlates with a decrease in the valence state of Mn according to X-ray absorption spectroscopy. These findings call for awareness regarding the use of electrode additives, since in some cases the extent of their impact on the properties of electrode films cannot be regarded as negligible

Operando Electrochemical Raman Spectroscopy

dvances in nanoscience and particularly in the fabrication of sophisticated nanostructures have led to substantial progress in the design of catalytic materials. Probing species at an aqueous interface during electrochemical reactions poses a great challenge to experimentalists and has raised considerable attention over the past decades, which is especially intriguing in the field of electrocatalysis. Several approaches for coupling electrochemical measurements to spectroscopic characterization of the electrode itself have been established and such experimental setups now represent state-of-the-art analytical techniques. Alongside with such developments a substantial improvement of already existing technologies for the analysis of nanostructures has been achieved, rendering them suitable to address the aforementioned challenges. A prime example is the case of Raman spectroscopy, which has been substantially developed in recent years toward the study of adsorbed molecules and/or the state of a material during catalytic reactions.Boosted by the discovery of the significant signal enhancement upon using nanostructured metals as substrates, Raman spectroscopy has evolved to become an appropriate tool for allowing the detection of Raman-active species in very small concentrations. Moreover, its versatility regarding operating conditions led to the development of operando electrochemical Raman spectroscopy (OERS), namely, Raman spectroscopic investigations of the electrochemical interfaces while electrochemical conversion under a controlled reaction rate is proceeding. Being electrochemists by training, we focus in this contribution on reactions linked to challenges in modern electrochemistry such as water electrolysis and CO2 conversion, and we highlight recent studies providing a comprehensive overview of developments important to the field. We aim to familiarize the reader with theoretical background of electrochemistry and Raman spectroscopy, and we broadly illustrate the implications of OERS for the understanding of fundamental electrochemical reactions and the elucidation of reaction mechanisms

What X-ray absorption spectroscopy can tell us about the active state of earth-abundant electrocatalysts for the oxygen evolution reaction

Chemical energy storage is an attractive solution to secure a sustainable energy supply. It requires an electrocatalyst to be implemented efficiently. In order to rationally improve the electrocatalyst materials and thereby the reaction efficiency, one must reveal the nature of the electrocatalyst under reaction conditions, i.e., its active state. For a better understanding of earth-abundant metal oxides as electrocatalysts for the oxygen evolution reaction (OER), the combination of electrochemical (EC) methods and X-ray absorption spectroscopy (XAS) has been very insightful and still holds untapped potential. Herein, we concisely introduce the basics of EC and XAS and provide the necessary framework to discuss changes that electrocatalytic materials undergo, presenting manganese oxides as examples. Such changes may occur during preparation and storage, during immersion in an electrolyte, as well as during application of potentials without or with catalytic reactions. We conclude with a concise summary of how EC and XAS are currently combined to elucidate the active state as well as an outlook on future opportunities to understand the mechanisms of electrocatalysis using combined operando EC-XAS experiments

MnFeNi‐based composite as a case study of a bifunctional oxygen electrocatalyst under dynamically changing electrode potentials

High-performance bifunctional electrocatalysts for the oxygen reduction (ORR) and oxygen evolution reaction (OER) are essential components in energy conversion and storage technologies. Yet, their poor reversibility hinders their applicability. A highly active ORR/OER catalyst, consisting of multiwalled carbon nanotubes-supported MnFeNiOx nanoparticles, was subjected to sequences of chronoamperometric steps alternating between the ORR, the OER and highly cathodic potentials (Ec). Rotating ring disk electrode methods revealed that applying Ec leads to a small increase in the current and peroxide species yield during the ORR while enhancing substantially the OER. X-ray absorption spectroscopy showed irreversible changes in the chemical state of MnFeNiOx correlating with its catalytic properties. The complexity of changes that a composite catalyst may undergo under varying potentials, the importance of monitoring product formation, and the convenience of using dynamic electrochemical sequences for the assessment of catalyst reversibility, as well as for the activation and/or restoration of their catalytic properties, are highlighted