Catalysis Sans Catalyst Loss: The Origins of Prolonged Stability of Graphene-Metal-Graphene Sandwich Architecture for Oxygen Reduction Reactions.

Over the past decades, the design of active catalysts has been the subject of intense research efforts. However, there has been significantly less deliberate emphasis on rationally designing a catalyst system with a prolonged stability. A major obstacle comes from the ambiguity behind how catalyst degrades. Several degradation mechanisms are proposed in literature,   but with a lack of systematic studies, the causal relations between degradation and those proposed mechanisms remain ambiguous. Here, a systematic study of a catalyst system comprising of small particles and single atoms of Pt sandwiched between graphene layers, GR/Pt/GR, is studied to  unravel the degradation mechanism of the studied electrocatalyst for oxygen reduction reaction(ORR). Catalyst suffers from atomic dissolution under ORR harsh acidic and oxidizing operation voltages. Single atoms trapped in point defects within the top graphene layer on their way hopping through toward the surface of GR/Pt/GR architecture. Trapping mechanism renders individual Pt atoms as single atom catalyst sites catalyzing ORR for thousands of cycles before washed away in the electrolyte. The GR/Pt/GR catalysts also compare favorably to state-of-the-art commercial Pt/C catalysts and demonstrates a rational design of a hybrid nanoarchitecture with a prolonged stability for thousands of operation cycles.

Spontaneous neonatal pulmonary arterial thrombosis - cases, mechanisms, and literature review.

Spontaneous pulmonary artery thrombosis in neonates is rare and can be life-threatening. Clinical presentation may mimic pulmonary hypertension or CHD. Further, not all children present with identifiable risk factors. We report the case of two infants with pulmonary artery thromboses who underwent rapid diagnosis and therapy, one with percutaneous intervention and the other with anticoagulation. We also conducted a literature review to highlight the importance of early identification and referral to a centre capable of performing appropriate medical and interventional therapies.

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction.

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

De-alloyed PtCu/C catalysts with enhanced electrocatalytic performance for the oxygen reduction reaction.

In electrochemical reactions, interactions between reaction intermediates and catalytic surfaces control the catalytic activity, and thereby require to be optimized. Electrochemical de-alloying of mixed-metal nanoparticles is a promising strategy to modify catalysts' surface chemistry and/or induce lattice strain to alter their electronic structure. Perfect design of the electrochemical de-alloying strategy to modify the catalyst's d-band center position can yield significant improvement on the catalytic performance of the oxygen reduction reaction (ORR). Herein, carbon supported PtCu catalysts are prepared by a simple polyol method followed by an electrochemical de-alloying treatment to form PtCu/C catalysts with a Pt-enriched porous shell with improved catalytic activity. Although the pristine PtCu/C catalyst exhibits a mass activity of 0.64 A mg-1Pt, the dissolution of Cu atoms from the catalyst surface after electrochemical de-alloying cycling leads to a significant enhancement in mass activity (1.19 A mg-1Pt), which is 400% better than that of state-of-the-art commercial Pt/C (0.24 A mg-1Pt). Furthermore, the de-alloyed PtCu/C-10 catalyst with a Pt-enriched shell delivers prolonged stability (loss of only 28.6% after 30 000 cycles), which is much better than that of Pt/C with a loss of 45.8%. By virtue of scanning transmission electron microscopy and elemental mapping experiments, the morphology and composition evolution of the catalysts could clearly be elucidated. This work helps in drawing a roadmap to design highly active and stable catalyst platforms for the ORR and relevant proton exchange membrane fuel cell applications.

Facile Room-Temperature Synthesis of a Highly Active and Robust Single-Crystal Pt Multipod Catalyst for Oxygen Reduction Reaction.

Economical production of highly active and robust Pt catalysts on a large scale is vital to the broad commercialization of polymer electrolyte membrane fuel cells. Here, we report a low-cost, one-pot process for large-scale synthesis of single-crystal Pt multipods with abundant high-index facets, in an aqueous solution without any template or surfactant. A composite consisting of the Pt multipods (40 wt %) and carbon displays a specific activity of 0.242 mA/cm2 and a mass activity of 0.109 A/mg at 0.9 V (versus a reversible hydrogen electrode) for oxygen reduction reaction, corresponding to ∼124% and ∼100% enhancement compared with those of the state-of-the-art commercial Pt/C catalyst (0.108 mA/cm2 and 0.054 A/mg). The single-crystal Pt multipods also show excellent stability when tested for 4500 cycles in a potential range of 0.6-1.1 V and another 2000 cycles in 0-1.2 V. More importantly, the superior performance of the Pt multipods/C catalyst is also demonstrated in a membrane electrode assembly (MEA), achieving a power density of 774 mW/cm2 (1.29 A/cm2) at 0.6 V and a peak power density of ∼1 W/cm2, representing 34% and 20% enhancement compared with those of a MEA based on the state-of-the-art commercial Pt/C catalyst (576 and 834 mW/cm2).

Atomic Structure and Dynamics of Epitaxial Platinum Bilayers on Graphene.

Platinum atomic layers grown on graphene were investigated by atomic resolution transmission electron microscopy (TEM). These TEM images reveal the epitaxial relationship between the atomically thin platinum layers and graphene, with two optimal epitaxies observed. The energetics of these epitaxies influences the grain structure of the platinum film, facilitating grain growth via in-plane rotation and assimilation of neighbor grains, rather than grain coarsening from the movement of grain boundaries. This growth process was enabled due to the availability of several possible low-energy intermediate states for the rotating grains, the Pt-Gr epitaxies, which are minima in surface energy, and coincident site lattice grain boundaries, which are minima in grain boundary energy. Density functional theory calculations reveal a complex interplay of considerations for minimizing the platinum grain energy, with free platinum edges also having an effect on the relative energetics. We thus find that the platinum atomic layer grains undergo significant reorientation to minimize interface energy (via epitaxy), grain boundary energy (via low-energy orientations), and free edge energy. These results will be important for the design of two-dimensional graphene-supported platinum catalysts and obtaining large-area uniform platinum atomic layer films and also provide fundamental experimental insight into the growth of heteroepitaxial thin films.

Sandwiched Graphene Interdiffusion Barrier for Preserving Au@Pt Atomically Thin Core@Shell Structure and the Resulting Oxygen Reduction Reaction Catalytic Activity.

The concept of a core-shell metallic structures, with a few atomic layers of the "shell" metal delineated from the "core" metal with atomic sharpness opens the door to a multitude of surface-driven materials properties that can be tuned. However, in practice, such architectures are difficult to retain due to the entropic cost of a segregated near-surface architecture, and the core and surface atoms inevitably mix through interdiffusion over time. We present here a systematic study of interdiffusion in a Pt on Au core-shell architecture and the role of an interrupting single layer of graphene sandwiched between them. The physical and chemical structure of the (near)surface is probed via mean-free-path tuned X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy (HRTEM), and electrochemistry (the oxygen reduction reaction, ORR). We find that at operating temperatures above 100 °C, there is potential for interdiffusion to occur between the primary and support metals of the core-shell catalyst system, which can diminish the catalyst activity toward ORR. The introduction of a single-layer graphene, as an interface between the core and shell metal layers, acts as a barrier that prevents unwanted surface alloying between the layered metals. HRTEM imaging shows that fully wetted Pt monolayers can be grown on a graphene template, allowing a high level of surface utilization of the catalyst material. We present how the use of graphene as a barrier to diffusion mitigates the loss of surface catalytic sites, showing much improved retention of Pt monolayer surface at elevated temperatures.

Defect engineering in 1D Ti-W oxide nanotube arrays and their correlated photoelectrochemical performance.

Understanding the nature of interfacial defects of materials is a critical undertaking for the design of high-performance hybrid electrodes for photocatalysis applications. Theoretical and computational endeavors to achieve this have touched boundaries far ahead of their experimental counterparts. However, to achieve any industrial benefit out of such studies, experimental validation needs to be systematically undertaken. In this sense, we present herein experimental insights into the synergistic relationship between the lattice position and oxidation state of tungsten ions inside a TiO2 lattice, and the respective nature of the created defect states. Consequently, a roadmap to tune the defect states in anodically-fabricated, ultrathin-walled W-doped TiO2 nanotubes is proposed. Annealing the nanotubes in different gas streams enabled the engineering of defects in such structures, as confirmed by XRD and XPS measurements. While annealing under hydrogen stream resulted in the formation of abundant Wn+ (n < 6) ions at the interstitial sites of the TiO2 lattice, oxygen- and air-annealing induced W6+ ions at substitutional sites. EIS and Mott-Schottky analyses indicated the formation of deep-natured trap states in the hydrogen-annealed samples, and predominantly shallow donating defect states in the oxygen- and air-annealed samples. Consequently, the photocatalytic performance of the latter was significantly higher than those of the hydrogen-annealed counterparts. Upon increasing the W content, photoelectrochemical performance deteriorated due to the formation of WO3 crystallites that hindered charge transfer through the photoanode, as evident from the structural and chemical characterization. To this end, this study validates the previous theoretical predictions on the detrimental effect of interstitial W ions. In addition, it sheds light on the importance of defect states and their nature for tuning the photoelectrochemical performance of the investigated materials.

Layer-by-layer evolution of structure, strain, and activity for the oxygen evolution reaction in graphene-templated Pt monolayers.

In this study, we explore the dimensional aspect of structure-driven surface properties of metal monolayers grown on a graphene/Au template. Here, surface limited redox replacement (SLRR) is used to provide precise layer-by-layer growth of Pt monolayers on graphene. We find that after a few iterations of SLRR, fully wetted 4-5 monolayer Pt films can be grown on graphene. Incorporating graphene at the Pt-Au interface modifies the growth mechanism, charge transfers, equilibrium interatomic distances, and associated strain of the synthesized Pt monolayers. We find that a single layer of sandwiched graphene is able to induce a 3.5% compressive strain on the Pt adlayer grown on it, and as a result, catalytic activity is increased due to a greater areal density of the Pt layers beyond face-centered-cubic close packing. At the same time, the sandwiched graphene does not obstruct vicinity effects of near-surface electron exchange between the substrate Au and adlayers Pt. X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) techniques are used to examine charge mediation across the Pt-graphene-Au junction and the local atomic arrangement as a function of the Pt adlayer dimension. Cyclic voltammetry (CV) and the oxygen reduction reaction (ORR) are used as probes to examine the electrochemically active area of Pt monolayers and catalyst activity, respectively. Results show that the inserted graphene monolayer results in increased activity for the Pt due to a graphene-induced compressive strain, as well as a higher resistance against loss of the catalytically active Pt surface.

Salivary progesterone and cervical length measurement as predictors of spontaneous preterm birth.

OBJECTIVE: To evaluate the efficacy of salivary progesterone, cervical length measurement in predicting preterm birth (PTB). METHODS: Prospective observational study included 240 pregnant women with gestational age (GA) 26-34 weeks classified into two equal groups; group one are high risk for PTB (those with symptoms of uterine contractions or history of one or more spontaneous preterm delivery or second trimester abortion) and group 2 are controls. RESULTS: There was a highly significant difference between the two study groups regarding GA at delivery (31.3 ± 3.75 in high risk versus 38.5 ± 1.3 in control), cervical length measured by transvaginal ultrasound (24.7 ± 8.6 in high risk versus 40.1 ± 4.67 in control) and salivary progesterone level (728.9 ± 222.3 in high risk versus 1099.9 ± 189.4 in control; p < 0.001). There was a statistically significant difference between levels of salivary progesterone at different GA among the high risk group (p value 0.035) but not in low risk group (p value 0.492). CL measurement showed a sensitivity of 71.5% with 100% specificity, 100% PPV, 69.97% NPV and accuracy of 83%, while salivary progesterone showed a sensitivity of 84% with 90% specificity, 89.8% PPV, 85.9% NPV and accuracy of 92.2%. CONCLUSION: The measurement of both salivary progesterone and cervical length are good predictors for development of PTB.

Life threatening angioedema in a patient on ACE inhibitor (ACEI) confined to the upper airway.

INTRODUCTION: ACE inhibitors accounts for 8% of all cases of angioneurotic edema and the overall incidence is 0.1 to 0.7% of patients on ACE inhibitors. It is a leading cause (20-40%) of emergency room visits in the US with angioedema. We report a case of angioedema caused by ACE inhibitors confined to the upper airway after four years on treatment with Lisinopril which persisted for three weeks and required endotracheal intubation and subsequent tracheostomy due to delayed resolution. This case is one of the rare cases presented as upper airway edema which persisted for a long time. PRESENTATION: A 60-year-old Sudanese male patient with osteoarthritis in both knees underwent bilateral total knee replacement under single-shot epidural anesthesia. He had significant past medical history of type II diabetes, bipolar affective disorder and hypertension managed with Lisinopril for the past four years. Postoperatively after 10 hours the patient desaturated and developed airway obstruction requiring intubation. Laryngoscopy revealed an edematous tongue and upper airway and vocal cords were not visualized. In view of this clinical picture a provisional diagnosis of angioedema secondary to Lisinopril was made and it was discontinued. CT scan of the neck and soft tissues revealed severe airway edema with snugly fitting endotracheal tube with no peritubal air. A repeat CT neck on the tenth postoperative day showed no signs of resolution and an elective tracheostomy was performed on the eleventh postoperative day. C1 inhibitor protein and C4 levels were assayed to exclude hereditary angioedema and were found to be within normal range. Decannulation of tracheostomy was done after airway edema resolved on the twenty-fourth postoperative day as confirmed by CT scan. Subsequently he was transferred to the ward and discharged home. CONCLUSION: ACEI induced angioedema is a well-recognized condition. Early diagnosis based on a high index of suspicion, immediate withdrawal of the offending drug followed by supportive therapy is the cornerstone of management.