An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation.

Transition metal carbides (TMCs) have demonstrated outstanding potential for utilization in a wide range of catalytic applications because of their inherent multifunctionality and tunable composition. However, the harsh conditions required to prepare these materials have limited the scope of synthetic control over their physical properties. The development of low-temperature, carburization-free routes to prepare TMCs would unlock the versatility of this class of materials, enhance our understanding of their physical properties, and enable their cost-effective production at industrial scales. Here, we report an exceptionally mild and scalable solution-phase synthesis route to phase-pure molybdenum carbide (α-MoC1-x) nanoparticles (NPs) in a continuous flow millifluidic reactor. We exploit the thermolytic decomposition of Mo(CO)6 in the presence of a surface-stabilizing ligand and a high boiling point solvent to yield MoC1-x NPs that are colloidally stable and resistant to bulk oxidation in air. To demonstrate the utility of this synthetic route to prepare catalytically active TMC NPs, we evaluated the thermochemical CO2 hydrogenation performance of α-MoC1-x NPs dispersed on an inert carbon support. The α-MoC1-x/C catalyst exhibited a 2-fold increase in both activity on a per-site basis and selectivity to C2+ products as compared to the bulk α-MoC1-x analogue.

Continuous Flow Methods of Fabricating Catalytically Active Metal Nanoparticles.

One of the obstacles preventing the commercialization of colloidal nanoparticle catalysts is the difficulty in fabricating these materials at scale while maintaining a high level of control over their resulting morphologies, and ultimately, their properties. Translation of batch-scale solution nanoparticle syntheses to continuous flow reactors has been identified as one method to address the scaling issue. The superior heat and mass transport afforded by the high surface-area-to-volume ratios of micro- and millifluidic channels allows for high control over reaction conditions and oftentimes results in decreased reaction times, higher yields, and/or more monodisperse size distributions compared to an analogous batch reaction. Furthermore, continuous flow reactors are automatable and have environmental health and safety benefits, making them practical for commercialization. Herein, a discussion of continuous flow methods, reactor design, and potential challenges is presented. A thorough account of the implementation of these technologies for the fabrication of catalytically active metal nanoparticles is reviewed for hydrogenation, electrocatalysis, and oxidation reactions.

Flow invariant droplet formation for stable parallel microreactors.

The translation of batch chemistries onto continuous flow platforms requires addressing the issues of consistent fluidic behaviour, channel fouling and high-throughput processing. Droplet microfluidic technologies reduce channel fouling and provide an improved level of control over heat and mass transfer to control reaction kinetics. However, in conventional geometries, the droplet size is sensitive to changes in flow rates. Here we report a three-dimensional droplet generating device that exhibits flow invariant behaviour and is robust to fluctuations in flow rate. In addition, the droplet generator is capable of producing droplet volumes spanning four orders of magnitude. We apply this device in a parallel network to synthesize platinum nanoparticles using an ionic liquid solvent, demonstrate reproducible synthesis after recycling the ionic liquid, and double the reaction yield compared with an analogous batch synthesis.

Sensory processing disorder in children ages birth-3 years born prematurely: a systematic review.

This systematic review of multidisciplinary literature synthesizes evidence of the prevalence and patterns of sensory processing disorder (SPD) in children ages birth-3 yr born preterm. Forty-five articles including physiological, behavioral, temperament, and SPD research met the inclusion criteria and provided 295 findings related to SPD-130 (44%) positive (evidence of SPD) and 165 (56%) negative (no evidence of SPD). The majority of findings related to sensory modulation disorder (SMD; 43% positive). The most prevalent subcategory of SMD was sensory overresponsivity (82% of findings positive). Evidence of sensory underresponsivity and sensory-seeking SMD, sensory discrimination disorder, and sensory-based motor disorder was limited. This study supports the education of neonatologists, pediatricians, and caregivers about the symptoms and potential consequences of SPD and helps justify the need for follow-up screening for SPD in children ages birth-3 yr born preterm. Research using measures based on sensory processing theory is needed.

Does language dominance affect cognitive performance in bilinguals? Lifespan evidence from preschoolers through older adults on card sorting, Simon, and metalinguistic tasks.

This study explores the extent to which a bilingual advantage can be observed for three tasks in an established population of fully fluent bilinguals from childhood through adulthood. Welsh-English simultaneous and early sequential bilinguals, as well as English monolinguals, aged 3 years through older adults, were tested on three sets of cognitive and executive function tasks. Bilinguals were Welsh-dominant, balanced, or English-dominant, with only Welsh, Welsh and English, or only English at home. Card sorting, Simon, and a metalinguistic judgment task (650, 557, and 354 participants, respectively) reveal little support for a bilingual advantage, either in relation to control or globally. Primarily there is no difference in performance across groups, but there is occasionally better performance by monolinguals or persons dominant in the language being tested, and in one case-in one condition and in one age group-lower performance by the monolinguals. The lack of evidence for a bilingual advantage in these simultaneous and early sequential bilinguals suggests the need for much closer scrutiny of what type of bilingual might demonstrate the reported effects, under what conditions, and why.