Covalent Transition Metal Borosilicides: Reaction Pathways in Molten Salts for Water Oxidation Electrocatalysis.

The properties of transition metal borides and silicides are intimately linked to the covalent character of the chemical bonds within their crystal structures. Bringing boron and silicon together within metal borosilicides can then engender different competing covalent networks and complex charge distributions. This situation results in unique structures and atomic environments, which can impact charge transport and catalytic properties. Metal borosilicides, however, hold the status of unusual exotic species, difficult to synthesize and with poor knowledge of their properties. Our strategy consists of developing a redox pathway to synthesize transition metal borosilicides in inorganic molten salts as high-temperature solvents. By studying the formation of Ni6Si2B, Co4.75Si2B, Fe5SiB2, and Mn5SiB2 with in situ X-ray diffraction, we highlight how new reaction routes, maintaining covalent structural building blocks, draw a general scheme of their formation. This pathway is driven by the covalence of the chemical bonds within the boron coordination framework. Next, we demonstrate high efficiency for water oxidation electrocatalysis, especially for Ni6Si2B. We ascribe the strongly increased resistance to corrosion, high stability, and electrocatalytic activity of the Ni6Si2B-derived material to three factors: (1) the two entangled boron and silicon covalent networks; (2) the ability to codope with boron and silicon an in situ generated catalytic layer; and (3) a rare electron enrichment of the transition metal by back-donation from boron atoms, previously unknown within this compound family. With this work, we then unveil a new chemical dimension for Earth-abundant water oxidation electrocatalysts by bringing to light a new family of materials.

Heterostructured Cobalt Silicide Nanocrystals: Synthesis in Molten Salts, Ferromagnetism, and Electrocatalysis.

Nanoscale heterostructures of covalent intermetallics should give birth to a wide range of interface-driven physical and chemical properties. Such a level of design however remains unattainable for most of these compounds, due to the difficulty to reach a crystalline order of covalent bonds at the moderate temperatures required for colloidal chemistry. Herein, we design heterostructured cobalt silicide nanoparticles to trigger magnetic and catalytic properties in silicon-based materials. Our strategy consists in controlling the diffusion of cobalt atoms into silicon nanoparticles, by reacting these particles in molten salts. By adjusting the temperature, we tune the conversion of the initial silicon particles toward homogeneous CoSi nanoparticles and core-shell nanoparticles made of a CoSi shell and a silicon-rich core. The increased interface-to-volume ratio of the CoSi component in the core-shell particles yields distinct properties compared to the bulk and homogeneous nanoparticles. First, the core-shell particles exhibit increased ferromagnetism, despite the bulk diamagnetic properties of cobalt monosilicide. Second, the core-shell nanoparticles act as efficient precatalysts for alkaline water oxidation, where the nanostructure is converted in situ into a layered cobalt silicon oxide/(oxy)hydroxide with high and stable oxygen evolution reaction (OER) electrocatalytic activity. This work demonstrates a route to design heterostructured nanocrystals of covalent intermetallic compounds and shows that these new structures exhibit very rich, yet poorly explored, interface-based physical properties and reactivity.

Revealing the Elusive Structure and Reactivity of Iron Boride α-FeB.

Crystal structures can strongly deviate from bulk states when confined into nanodomains. These deviations may deeply affect properties and reactivity and then call for a close examination. In this work, we address the case where extended crystal defects spread through a whole solid and then yield an aperiodic structure and specific reactivity. We focus on iron boride, α-FeB, whose structure has not been elucidated yet, thus hindering the understanding of its properties. We synthesize the two known phases, α-FeB and ß-FeB, in molten salts at 600 and 1100 °C, respectively. The experimental X-ray diffraction (XRD) data cannot be satisfactorily accounted for by a periodic crystal structure. We then model the compound as a stochastic assembly of layers of two structure types. Refinement of the powder XRD pattern by considering the explicit scattering interference of the different layers allows quantitative evaluation of the size of these domains and of the stacking faults between them. We, therefore, demonstrate that α-FeB is an intergrowth of nanometer-thick slabs of two structure types, ß-FeB and CrB-type structures, in similar proportions. We finally discuss the implications of this novel structure on the reactivity of the material and its ability to perform insertion reactions by comparing the reactivities of α-FeB and ß-FeB as reagents in the synthesis of a model layered material: Fe2AlB2. Using synchrotron-based in situ X-ray diffraction, we elucidate the mechanisms of the formation of Fe2AlB2. We highlight the higher reactivity of the intergrowth α-FeB in agreement with structural relationships.

Adolescents' preference for later school start times.

As the chronotype delays progressively throughout puberty, early morning school start times (SSTs) contradict the sleep biology of adolescents. Various studies have demonstrated beneficial effects of later SSTs on sleep and health; however, adolescents' preferences for SSTs have to date never been investigated in detail. The present online survey study aimed to fill this gap and explored influencing factors. A total of 17 high schools in the Canton of Zurich, Switzerland, circulated the survey among their students. Participants were included if they reported their sex, age, and school (n = 5,308). Students indicated whether they preferred later SSTs. Additionally, five predictor blocks were assessed: sociodemographic, school-related, sleep, leisure-time, and health-related characteristics. We applied multivariate logistic regression models with fixed and random effects to predict the preference. The mean (SD) age of the students was 16.09 (1.76) years (65.1% female). The majority (63.2%) endorsed later SSTs with a preferred delay of 55 min (interquartile range 25-75 min). In the multilevel analysis (n = 2,627), sex, mother tongue, sleep characteristics, mobile device use at bedtime, caffeine consumption, and health-related quality of life were significant predictors for the preference. Hence, the majority of adolescents preferred later SSTs, and especially those with sleep or health-related problems. These characteristics have been consistently shown to improve after delaying SSTs. Thus, also from adolescents' view, later SSTs should be considered to improve the adolescents' health.

Association Between Homeschooling and Adolescent Sleep Duration and Health During COVID-19 Pandemic High School Closures.

Importance: Although negative associations of COVID-19 pandemic high school closures with adolescents' health have been demonstrated repeatedly, some research has reported a beneficial association of these closures with adolescents' sleep. The present study was, to our knowledge, the first to combine both perspectives. Objective: To investigate associations between adolescents' sleep and health-related characteristics during COVID-19 pandemic school closures in Switzerland. Design, Setting, and Participants: This survey study used cross-sectional online surveys circulated among the students of 21 public high schools in Zurich, Switzerland. The control sample completed the survey under regular, prepandemic conditions (May to July 2017) and the lockdown sample during school closures (May to June 2020). Survey respondents were included in the study if they provided their sex, age, and school. Exposures: High school closures during the first COVID-19 pandemic wave in Switzerland (March 13 to June 6, 2020). Main Outcomes and Measures: Sleep-wake patterns, health-related quality of life (HRQoL, assessed by the KIDSCREEN-10 questionnaire), substance use (caffeine, alcohol, and nicotine), and depressive symptoms (lockdown sample only; assessed using the withdrawn/depressed scale from the Youth Self Report). Multilevel regression models were used to assess sample differences and associations of health-related characteristics with sleep duration and depressive symptoms. Results: The total sample consisted of 8972 students, including 5308 (59.2%) in the control sample (3454 [65.1%] female) and 3664 (40.8%) in the lockdown sample (2429 [66.3%] female); the median age in both samples was 16 years (IQR, 15-17 years). During school closures, the sleep period on scheduled days was 75 minutes longer (semipartial R2 statistic [R2ß*], 0.238; 95% CI, 0.222-0.254; P < .001) and the students had better HRQoL (R2ß*, 0.007; 95% CI, 0.004-0.012; P < .001) and less consumption of caffeine (R2ß*, 0.010; 95% CI, 0.006-0.015; P < .001) and alcohol (R2ß*, 0.014; 95% CI, 0.008-0.022; P < .001). Longer sleep duration was associated with better HRQoL (R2ß*, 0.027; 95% CI, 0.020-0.034; P < .001) and less caffeine consumption (R2ß*, 0.013; 95% CI, 0.009-0.019; P < .001). In the lockdown sample, an inverse association was found between depressive symptoms and HRQoL (R2ß*, 0.285; 95% CI, 0.260-.0311; P < .001) and a positive association was found with caffeine consumption (R2ß*, 0.003; 95% CI, 0.000-0.008; P = .01). Conclusions and Relevance: In this survey study, 2 opposing associations between school closures and adolescents' health were identified: a negative association with psychological distress and a beneficial association with increased sleep duration. These findings should be considered when evaluating and implementing school closures. Furthermore, the findings provide support for delaying school start times for adolescents.