A Data-Driven Approach to Molten Salt Synthesis of N-Rich Carbon Adsorbents for Selective CO2 Capture.

Applying a design of experiments methodology to the molten salt synthesis of nanoporous carbons enables inverse design and optimization of nitrogen (N)-rich carbon adsorbents with excellent CO2 /N2 selectivity and appreciable CO2 capacity for carbon capture via swing adsorption from dilute gas mixtures such as natural gas combined cycle flue gas. This data-driven study reveals fundamental structure-function relationships between the synthesis conditions, physicochemical properties, and achievable selective adsorption performance of N-rich nanoporous carbons derived from molten salt synthesis for CO2 capture. Taking advantage of size-sieving separation of CO2 (3.30 Å) from N2 (3.64 Å) within the turbostratic nanostructure of these N-rich carbons, while limiting deleterious N2 adsorption in a weaker adsorption site that harms selectivity, enables a large CO2 capacity (0.73 mmol g-1 at 30.4 Torr and 30 °C) with noteworthy concurrent CO2 /N2 selectivity as predicted by the ideal adsorbed solution theory (SIAST = 246) with an adsorbed phase purity of 91% from a simulated gas stream containing only 4% CO2 . Optimized N-rich porous carbons, with good physicochemical stability, low cost, and moderate regeneration energy, can achieve performance for selective CO2 adsorption that competes with other classes of advanced porous materials such as chemisorbing zeolites and functionalized metal-organic frameworks.

In Situ Engineering of Inorganic-Rich Solid Electrolyte Interphases via Anion Choice Enables Stable, Lithium Anodes.

The discovery of liquid battery electrolytes that facilitate the formation of stable solid electrolyte interphases (SEIs) to mitigate dendrite formation is imperative to enable lithium anodes in next-generation energy-dense batteries. Compared to traditional electrolyte solvents, tetrahydrofuran (THF)-based electrolyte systems have demonstrated great success in enabling high-stability lithium anodes by encouraging the decomposition of anions (instead of organic solvent) and thus generating inorganic-rich SEIs. Herein, by employing a variety of different lithium salts (i.e., LiPF6, LiTFSI, LiFSI, and LiDFOB), it is demonstrated that electrolyte anions modulate the inorganic composition and resulting properties of the SEI. Through novel analytical time-of-flight secondary-ion mass spectrometry methods, such as hierarchical clustering of depth profiles and compositional analysis using integrated yields, the chemical composition and morphology of the SEIs generated from each electrolyte system are examined. Notably, the LiDFOB electrolyte provides an exceptionally stable system to enable lithium anodes, delivering >1500 cycles at a current density of 0.5 mAh g-1 and a capacity of 0.5 mAh g-1 in symmetrical cells. Furthermore, Li//LFP cells using this electrolyte demonstrate high-rate, reversible lithium storage, supplying 139 mAh g(LFP) -1 at C/2 (≈0.991 mAh cm-2 , @ 0.61 mA cm-2 ) with 87.5% capacity retention over 300 cycles (average Coulombic efficiency >99.86%).

Camphene-Assisted Fabrication of Free-Standing Lithium-Ion Battery Electrode Composites.

Free-standing electrode (FSE) architectures hold the potential to dramatically increase the gravimetric and volumetric energy density of lithium-ion batteries (LIBs) by eliminating the parasitic dead weight and volume associated with traditional metal foil current collectors. However, current FSE fabrication methods suffer from insufficient mechanical stability, electrochemical performance, or industrial adoptability. Here, we demonstrate a scalable camphene-assisted fabrication method that allows simultaneous casting and templating of FSEs comprising common LIB materials with a performance superior to their foil-cast counterparts. These porous, lightweight, and robust electrodes simultaneously enable enhanced rate performance by improving the mass and ion transport within the percolating conductive carbon pore network and eliminating current collectors for efficient and stable Li+ storage (>1000 cycles in half-cells) at increased gravimetric and areal energy densities. Compared to conventional foil-cast counterparts, the camphene-derived electrodes exhibit ∼1.5× enhanced gravimetric energy density, increased rate capability, and improved capacity retention in coin-cell configurations. A full cell containing both a free-standing anode and cathode was cycled for over 250 cycles with greater than 80% capacity retention at an areal capacity of 0.73 mA h/cm2. This active-material-agnostic electrode fabrication method holds potential to tailor the morphology of flexible, current-collector-free electrodes, thus enabling LIBs to be optimized for high power or high energy density Li+ storage. Furthermore, this platform provides an electrode fabrication method that is applicable to other electrochemical technologies and advanced manufacturing methods.

Calcium Poly(Heptazine Imide): A Covalent Heptazine Framework for Selective CO2 Adsorption.

Potassium poly(heptazine imide) (KPHI) has recently garnered attention as a crystalline carbon nitride framework with considerable photoelectrochemical activity. Here, we report a Ca2+-complexed analogue of PHI: calcium poly(heptazine imide) (CaPHI). Despite similar polymer backbone, CaPHI and KPHI exhibit markedly different crystal structures. Spectroscopic, crystallographic, and physisorptive characterization reveal that Ca2+ acts as a structure-directing agent to transform melon-based carbon nitride to crystalline CaPHI with ordered pore channels, extended visible light absorption, and altered band structure as compared to KPHI. Upon acid washing, protons replace Ca2+ atoms in CaPHI to yield H+/CaPHI and enhance porosity without disrupting crystal structure. Further, these proton-exchanged PHI frameworks exhibit large adsorption affinity for CO2 and exceptional performance for selective carbon capture from dilute streams. Compared to a state-of-the-art metal organic framework, UTSA-16, H+/CaPHI exhibits more than twice the selectivity (∼300 vs ∼120) and working capacity (∼1.2 mmol g-1 vs ∼0.5 mmol g-1) for a feed of 4% CO2 (1 bar, 30 °C).

Anodized Nickel Foam for Oxygen Evolution Reaction in Fe-Free and Unpurified Alkaline Electrolytes at High Current Densities.

To achieve practically high electrocatalytic performance for the oxygen evolution reaction (OER), the active surface area should be maximized without severely compromising electron and mass transport throughout the catalyst electrode. Though the importance of electron and mass transport has been studied using low surface area catalysts under low current densities (∼tens of mA/cm2), the transport properties of large surface area catalysts under high operating current densities (∼500 mA/cm2) for practical OER catalysis have rarely been explored. Herein, three-dimensional (3D) hierarchically porous anodized nickel foams (ANFs) with large and variable surface areas were synthesized via electrochemical anodization of 3D nickel foam and applied as OER electrocatalysts in Fe-free and unpurified KOH electrolytes. Using Fe-free and in situ Fe-doped ANF that were prepared in Fe-free and unpurified electrolytes, respectively, we investigated the interdependent effects of active surface area and transport properties on OER activity under practically high current densities. While activity increased linearly with active surface area for Fe-free ANF, the activity of Fe-doped ANF showed a nonlinear increase with active surface area due to lower electrocatalytic activity enhancement. Detailed investigations on the possible factors (Fe incorporation, mass transport, and electron transport) identified that electron transport limitations played the major role in restricting the activity enhancement with increasing active surface area for Fe-doped ANF, although Fe-doped ANF has electron transport properties better than those of Fe-free ANF. This study exemplifies the growing significance of electron transport properties in large surface area catalysts, especially those with superb intrinsic catalytic activity and high operating current density.

Neurosyphilis: Still prevalent and overlooked in an at risk population.

BACKGROUND: Neurosyphilis (NS) presents with a variety of clinical syndromes that can be attributed to other aetiologies due to difficulties in its diagnosis. We reviewed all cases of NS from the "Top End" of the Australian Northern Territory over a ten-year period to assess incidence, clinical and laboratory manifestations. METHODS: Patient data (2007-2016) were extracted from hospital records, centralised laboratory data and Northern Territory Centre for Disease Control records. Clinical records of patients with clinically suspected NS were reviewed. A diagnosis of NS was made based on the 2014 US CDC criteria. Results were also recategorized based on the 2018 US CDC criteria. RESULTS: The population of the "Top End" is 185,570, of whom 26.2% are Indigenous. A positive TPPA was recorded in 3126 individuals. A total of 75 (2.4%) of TPPA positive patients had a lumbar puncture (LP), of whom 25 (35%) were diagnosed with NS (9 definite, 16 probable). Dementia was the most common manifestation (58.3%), followed by epilepsy (16.7%), psychosis (12.5%), tabes dorsalis (12.5%) and meningovascular syphilis (8.3%). 63% of probable NS cases were not treated appropriately due to a negative CSF VDRL. Despite increased specificity of the 2018 US CDC criteria, 70% of patient in the probable NS group were not treated appropriately. The overall annual incidence [95%CI] of NS was 2.47[1.28-4.31] per 100 000py in the Indigenous population and 0.95[0.50-1.62] in the non-Indigenous population (rate ratio = 2.60 [1.19-5.70];p = 0.017). CONCLUSION: Neurosyphilis is frequently reported in the NT, particularly in Indigenous populations. Disturbingly, 60% of probable neurosyphilis patients based on the 2014 criteria, and 70% based on the 2018 criteria with were not treated appropriately. It is critical that clinicians should be aware of the diagnosis of NS and treat patients appropriately.

Effect of Selenium Content on Nickel Sulfoselenide-Derived Nickel (Oxy)hydroxide Electrocatalysts for Water Oxidation.

An efficient and inexpensive electrocatalyst for the oxygen evolution reaction (OER) must be found in order to improve the viability of hydrogen fuel production via water electrolysis. Recent work has indicated that nickel chalcogenide materials show promise as electrocatalysts for this reaction and that their performance can be further enhanced with the generation of ternary, bimetallic chalcogenides (i.e., Ni1-aMaX2); however, relatively few studies have investigated ternary chalcogenides created through the addition of a second chalcogen (i.e., NiX2-aYa). To address this, we studied a series of Se-modified Ni3S2 composites for use as OER electrocatalysts in alkaline solution. We found that the addition of Se results in the creation of Ni3S2/NiSe composites composed of cross-doped metal chalcogenides and show that the addition of 10% Se reduces the overpotential required to reach a current density of 10 mA/cm2 by 40 mV versus a pure nickel sulfide material. Chemical analysis of the composites' surfaces shows a reduction in the amount of nickel oxide species with Se incorporation, which is supported by transmission electron microscopy; this reduction is correlated with a decrease in the OER overpotentials measured for these samples. Together, our results suggest that the incorporation of Se into Ni3S2 creates a more conductive material with a less-oxidized surface that is more electrocatalytically active and resistant to further oxidation. Importantly, oxidation does still occur, and the active catalyst is most likely a nickel (oxy)hydroxide surrounding a crystalline, conductive Ni3S2-xSex core.

Carbon Nitride Transforms into a High Lithium Storage Capacity Nitrogen-Rich Carbon.

We describe here the metal-templated transformation of carbon nitride (C3N4) into nitrogen-containing carbons as anodes for Li-ion batteries (LIBs). Changing the template from the carbon- and nitrogen-immiscible Cu powder to the carbon- and nitrogen-miscible Fe powder yields different carbons; while Fe templating produces graphitized carbons of low (<10%) nitrogen content and moderate pore volume, Cu templating yields high defect-density carbons of high (32-24%) nitrogen content and larger pore volume. The Li+ storage capacity of the high nitrogen content and larger pore volume Cu-templated carbons exceeds that of the more graphitic Fe-templated carbons due to added contribution from Li+ insertion/extraction from pores and defects and to reversible faradaic Li+ reaction with nitrogen atoms. The Cu-templated carbon annealed at 750 °C delivers the highest specific capacity of 900 mAh g-1 at 0.1 A g-1 and 275 mAh g-1 at 20 A g-1, while also achieving a 96% capacity retention after 2000 cycles at 2 A g-1. The fabrication of higher mass loading electrodes (4.5 mg cm-2) provided a maximum areal capacity of 2.6 mAh cm-2 at 0.45 mA cm-2 (0.1 A g-1), comparable to the capacities of commercial LIB cells and favorable compared to other reported carbon materials.

Adverse outcome after incident stroke hospitalization for Indigenous and non-Indigenous Australians in the Northern Territory.

BACKGROUND: Survival after a stroke is lower for Indigenous than other stroke patients in Australia. It is not known whether recurrence is more common for Indigenous patients, or whether their higher prevalence of comorbidity affects their lower survival. AIMS: This study aimed to investigate the stroke recurrence and role of comorbidities in adverse stroke outcomes (recurrence and death) for Indigenous compared with other Australians. METHODS: A retrospective cohort study of first hospitalization for stroke (n = 2105) recorded in Northern Territory hospital inpatient data between 1996 and 2011 was conducted. For the multivariable analyses of adverse outcomes, logistic regression was used for case fatality and competing risk analysis for recurrent stroke and long-term death. Comorbidities (identified from inpatient diagnosis data) were analyzed using the Charlson Comorbidity Index (modified for stroke outcomes). RESULTS: Prevalence of comorbidities, case fatality, incidence of re-hospitalization for recurrent stroke, and long-term death rate were higher for Indigenous than non-Indigenous stroke patients. Adjustment for comorbidity in multivariable analyses considerably reduced Indigenous patients' excess risk for case fatality (odds ratio: 1·25, 0·88-1·78) and long-term death (standard hazard ratio: 1·27, 1·01-1·61) (but not recurrence), implying that their excess risk of death was in part due to higher comorbidity prevalence. CONCLUSION: Indigenous stroke patients have higher prevalence of comorbidities than non-Indigenous stroke patients, which explained part of the disparity in both case fatality and long-term survival but did not explain the disparity in stroke recurrence at all.

Murray Valley encephalitis: a review of clinical features, diagnosis and treatment.

Murray Valley encephalitis virus (MVEV) is a mosquito-borne virus that is found across Australia, Papua New Guinea and Irian Jaya. MVEV is endemic to northern Australia and causes occasional outbreaks across south-eastern Australia. 2011 saw a dramatic increase in MVEV activity in endemic regions and the re-emergence of MVEV in south-eastern Australia. This followed significant regional flooding and increased numbers of the main mosquito vector, Culex annulirostris, and was evident from the widespread seroconversion of sentinel chickens, fatalities among horses and several cases in humans, resulting in at least three deaths. The last major outbreak in Australia was in 1974, during which 58 cases were identified and the mortality rate was about 20%. With the potential for a further outbreak of MVEV in the 2011-2012 summer and following autumn, we highlight the importance of this disease, its clinical characteristics and radiological and laboratory features. We present a suspected but unproven case of MVEV infection to illustrate some of the challenges in clinical management. It remains difficult to establish an early diagnosis of MVEV infection, and there is a lack of proven therapeutic options.

West nile virus (Kunjin subtype) disease in the northern territory of Australia--a case of encephalitis and review of all reported cases.

West Nile virus Kunjin subtype (WNV/KUNV) is enzootic across the tropical north of Australia, with epizootic spread into other jurisdictions. The clinical spectrum of illness in humans is poorly described. We report a clinical case of WNV/KUNV encephalitis and performed a retrospective chart audit of all cases of WNV/KUNV notified in the Northern Territory from 1992 to 2010. Thirteen cases of WNV/KUNV disease were identified; case notes were available for 10 of these presentations. Six of these patients had confirmed infection and presented with neuroinvasive illness, whereas the other four suspect cases comprised three cases with arthralgia, myalgia, and/or rash and one case with fever alone. On the available evidence, WNV/KUNV is of lower virulence compared with the New York 1999 strain. Difficulties in serological diagnosis, especially when paired acute and convalescent sera are not available, may adversely impact the accuracy of the epidemiological and clinical understanding of this virus.

Murray Valley encephalitis in an adult traveller complicated by long-term flaccid paralysis: case report and review of the literature.

Murray Valley encephalitis (MVE) virus, a mosquito-borne flavivirus, is the most common cause of viral encephalitis in the tropical 'Top End' of northern Australia. Clinical encephalitis due to MVE virus has a mortality rate of approximately 30%, with a similar proportion of patients being left with significant neurological deficits. We report the case of a 25-year-old man from the UK who acquired MVE while travelling through northern Australia. He required prolonged admission to the Intensive Care Unit and several years later remains partly ventilator-dependent, with flaccid quadriparesis. To our knowledge, this is the first reported case of MVE virus-induced flaccid paralysis in an adult in northern Australia, although it is well described in children. Paralysis was thought to be due to anterior horn cell involvement in the spinal cord and extensive bilateral thalamic destruction, both of which are well recognised complications of infection with MVE virus. Cases of flaccid paralysis with similar pathology have been described following infection with the related flavivirus Japanese encephalitis virus as well as more recently with West Nile virus. Our case highlights the potential severity of flavivirus-induced encephalitis and the importance of avoiding mosquito bites while travelling through endemic areas.