Gram-scale bottom-up flash graphene synthesis.

Most bulk-scale graphene is produced by a top-down approach, exfoliating graphite, which often requires large amounts of solvent with high-energy mixing, shearing, sonication or electrochemical treatment1-3. Although chemical oxidation of graphite to graphene oxide promotes exfoliation, it requires harsh oxidants and leaves the graphene with a defective perforated structure after the subsequent reduction step3,4. Bottom-up synthesis of high-quality graphene is often restricted to ultrasmall amounts if performed by chemical vapour deposition or advanced synthetic organic methods, or it provides a defect-ridden structure if carried out in bulk solution4-6. Here we show that flash Joule heating of inexpensive carbon sources-such as coal, petroleum coke, biochar, carbon black, discarded food, rubber tyres and mixed plastic waste-can afford gram-scale quantities of graphene in less than one second. The product, named flash graphene (FG) after the process used to produce it, shows turbostratic arrangement (that is, little order) between the stacked graphene layers. FG synthesis uses no furnace and no solvents or reactive gases. Yields depend on the carbon content of the source; when using a high-carbon source, such as carbon black, anthracitic coal or calcined coke, yields can range from 80 to 90 per cent with carbon purity greater than 99 per cent. No purification steps are necessary. Raman spectroscopy analysis shows a low-intensity or absent D band for FG, indicating that FG has among the lowest defect concentrations reported so far for graphene, and confirms the turbostratic stacking of FG, which is clearly distinguished from turbostratic graphite. The disordered orientation of FG layers facilitates its rapid exfoliation upon mixing during composite formation. The electric energy cost for FG synthesis is only about 7.2 kilojoules per gram, which could render FG suitable for use in bulk composites of plastic, metals, plywood, concrete and other building materials.

Electric Field Effects in Flash Joule Heating Synthesis.

Flash Joule heating has emerged as an ultrafast, scalable, and versatile synthesis method for nanomaterials, such as graphene. Here, we experimentally and theoretically deconvolute the contributions of thermal and electrical processes to the synthesis of graphene by flash Joule heating. While traditional methods of graphene synthesis involve purely chemical or thermal driving forces, our results show that the presence of charge and the resulting electric field in a graphene precursor catalyze the formation of graphene. Furthermore, modulation of the current or the pulse width affords the ability to control the three-step phase transition of the material from amorphous carbon to turbostratic graphene and finally to ordered (AB and ABC-stacked) graphene and graphite. Finally, density functional theory simulations reveal that the presence of a charge- and current-induced electric field inside the graphene precursor facilitates phase transition by lowering the activation energy of the reaction. These results demonstrate that the passage of electrical current through a solid sample can directly drive nanocrystal nucleation in flash Joule heating, an insight that may inform future Joule heating or other electrical synthesis strategies.

Cathode Interface Construction by Rapid Sintering in Solid-State Batteries.

Solid-state batteries (SSBs) are poised to replace traditional organic liquid-electrolyte lithium-ion batteries due to their higher safety and energy density. Oxide-based solid electrolytes (SEs) are particularly attractive for their stability in air and inability to ignite during thermal runaway. However, achieving high-performance in oxide-based SSBs requires the development of an intimate and robust SE-cathode interface to overcome typically large interfacial resistances. The transition interphase should be both physically and chemically active. This study presents a thin, conductive interphase constructed between lithium aluminum titanium phosphate and lithium cobalt oxide using a rapid sintering method that modifies the interphase within 10 s. The rapid heating and cooling rates restrict side reactions and interdiffusion on the interface. SSBs with thick composite cathodes demonstrate a high initial capacity of ≈120 mAh g-1 over 200 cycles at room temperature. Furthermore, the rapid sintering method can be extended to other cathode systems under similar conditions. These findings highlight the importance of constructing an appropriate SE-cathode interface and provide insight into designing practical SSBs.

Repeatability and Reproducibility of Corneoscleral Topography Measured With Scheimpflug Imaging in Keratoconus and Control Eyes.

OBJECTIVES: To determine and compare the repeatability and reproducibility of anterior scleral parameters measured by the corneoscleral profile (CSP) module of Pentacam in keratoconus (KC) and control eyes. METHODS: This is a prospective observational study. Thirty KC participants (30 eyes) and 24 control participants (24 eyes) were examined three times using the CSP. Sagittal height mean (SHM), sagittal height astigmatism (SHA), and mean bulbar slope (BSM) were measured in 12 mm and 16 mm chord lengths. The repeatability and reproducibility of these measurements were also assessed. Coefficients of variation (CoV), intraclass correlation coefficient (ICC), coefficient of repeatability (CoR1), and coefficient of reproducibility (CoR2) were adopted to assess the reliability. RESULTS: In the KC and control groups, SHM showed high repeatability and reproducibility (coefficients of variation [CoVs]≤0.96%, intraclass correlation coefficient [ICCs]≥0.97), and SHM of control eyes showed higher repeatability and reproducibility than that of KC eyes at 12 mm chord length (KC group, CoRs ranged from 35.56 µm to 43.52 µm, control group, ranged from 23.50 µm to 30.31 µm) and 16 mm chord length (KC group, CoRs ranged from 79.54 µm to 81.58 µm, control group, ranged from 48.25 µm to 66.10 µm). Mean bulbar slope also showed high repeatability and reproducibility (CoVs≤3.65%, CoRs≤2.64). Furthermore, the SHA of control eyes showed higher repeatability and reproducibility when compared with KC eyes (control group: CoVs≤29.95%, KC group: CoVs≥32.67%). CONCLUSIONS: Keratoconus and control eyes demonstrated high repeatability and reproducibility when using CSP measurements, which may prove helpful in fitting contact lenses.

Enhanced degradation of organic contaminants using catalytic activity of carbonaceous structures: A strategy for the reuse of exhausted sorbents.

Generation of hydroxyl radicals (⋅OH) is the basis of advanced oxidation process (AOP). This study investigates the catalytic activity of microporous carbonaceous structure for in-situ generation of ⋅OH radicals. Biochar (BC) was selected as a representative of carbon materials with a graphitic structure. The work aims at assessing the impact of BC structure on the activation of H2O2, the reinforcement of the persistent free radicals (PFRs) in BC using heavy metal complexes, and the subsequent AOP. Accordingly, three different biochars (raw, chemically- and physiochemically-activated BCs) were used for adsorption of two metal ions (nickel and lead) and the degradation of phenol (100 mg/L) through AOP. The results demonstrated four outcomes: (1) The structure of carbon material, the identity and the quantity of the metal complexes in the structure play the key roles in the AOP process. (2) the quantity of PFRs on BC significantly increased (by 200%) with structural activation and metal loading. (3) Though the Pb-loaded BC contained a larger quantity of PFRs, Ni-loaded BC exhibited a higher catalytic activity. (4) The degradation efficiency values for phenol by modified biochar in the presence of H2O2 was 80.3%, while the removal efficiency was found to be 17% and 22% in the two control tests, with H2O2 (no BC) and with BC (no H2O2), respectively. Overall, the work proposes a new approach for dual applications of carbonaceous structures; adsorption of metal ions and treatment of organic contaminants through in-situ chemical oxidation (ISCO).

Crystal-Field Tuning of Photoluminescence in Two-Dimensional Materials with Embedded Lanthanide Ions.

Lanthanide (Ln) group elements have been attracting considerable attention owing to the distinct optical properties. The crystal-field surroundings of Ln ions in the host materials can determine their energy level splitting, which is of vital importance to tailor their optical properties. 2D MoS2 single crystals were utilized as the host material to embed Eu3+ and energy-level splitting was achieved for tuning its photoluminescence (PL). The high anisotropy of the 2D host materials makes them distort the degenerate orbitals of the Ln ions more efficiently than the symmetrical bulk host materials. A significant red-shift of the PL peak for Eu3+ was observed. The strategy for tailoring the energy level splitting of Ln ions by the highly designable 2D material crystal field provides a new method to extend their optical properties.

[Effects of Shenxiong pill on infarct brain volumes and NF-kappaB expression in SD rats with middle cerebral artery occlusion (MCAO)].

OBJECTIVE: To investigate the effects of Shenxiong Pill on the infarct volume and expression of NF-kappaB in brains of rats with middle cerebral artery occlusion. METHODS: 169 SD rats were randomly divided into five groups: normal group, sham group, model group, cyclophosphamide group and Shenxiong Pill group. MCAO rat models were established by string ligation (for model, cyclophosphamide-treated and Shenxiong-treated groups). Rats in the Shenxiong Pill group was further randomly divided into sub-groups, receiving a range of high dose treatment (5 to 20 times of clinical dosage). Brains of the rats were examined 48 h or 72 h after interventions in a random order. Image processing software was used in the calculation of volume of cerebral infarction. Conventional HE staining was used for observation of brain tissue. Immunohistochemical method was used to determine NF-kappaB expression. RESULTS: Compared with the model group, rats treated with Shenxiong Pill and cyclophosphamide had lower infarct brain volumes (P < 0.05). NF-kappaB positive inflammatory cells were not found in the normal and sham groups. But the MCAO model rats had increased numbers of NF-kappaB positive inflammatory cells and higher integral optical density of NF-kappaB over time. Compared with the model group, lower numbers and expression of NF-kappaB positive inflammatory cells were found in those treated with Shenxiong Pill (P<0. 05). Higher dosage of Shenxiong was associated with lower numbers and expression of NF-gB inflammatory cells (P<0. 05). CONCLUSION: Shenxiong Pill can reduce pathological damage to brains as a result of cerebral ischemia, possibly through inhibiting the expression and activation of NF-kappaB.

Automated Laboratory Kilogram-Scale Graphene Production from Coal.

The flash Joule heating (FJH) method converts many carbon feedstocks into graphene in milliseconds to seconds using an electrical pulse. This opens an opportunity for processing low or negative value resources, such as coal and plastic waste, into high value graphene. Here, a lab-scale automation FJH system that allows the synthesis of 1.1 kg of turbostratic flash graphene from coal-based metallurgical coke (MC) in 1.5 h is demonstrated. The process is based on the automated conversion of 5.7 g of MC per batch using an electrical pulse width modulation system to conduct the bottom-up upcycle of MC into flash graphene. This study then compare this method to two other scalable graphene synthesis techniques by both a life cycle assessment and a technoeconomic assessment.

Oxidized Activated Charcoal Nanozymes: Synthesis, and Optimization for In Vitro and In Vivo Bioactivity for Traumatic Brain Injury.

Carbon-based superoxide dismutase (SOD) mimetic nanozymes have recently been employed as promising antioxidant nanotherapeutics due to their distinct properties. The structural features responsible for the efficacy of these nanomaterials as antioxidants are, however, poorly understood. Here, the process-structure-property-performance properties of coconut-derived oxidized activated charcoal (cOAC) nano-SOD mimetics are studied by analyzing how modifications to the nanomaterial's synthesis impact the size, as well as the elemental and electrochemical properties of the particles. These properties are then correlated to the in vitro antioxidant bioactivity of poly(ethylene glycol)-functionalized cOACs (PEG-cOAC). Chemical oxidative treatment methods that afford smaller, more homogeneous cOAC nanoparticles with higher levels of quinone functionalization show enhanced protection against oxidative damage in bEnd.3 murine endothelioma cells. In an in vivo rat model of mild traumatic brain injury (mTBI) and oxidative vascular injury, PEG-cOACs restore cerebral perfusion rapidly to the same extent as the former nanotube-derived PEG-hydrophilic carbon clusters (PEG-HCCs) with a single intravenous injection. These findings provide a deeper understanding of how carbon nanozyme syntheses can be tailored for improved antioxidant bioactivity, and set the stage for translation of medical applications.

Kinetically Controlled Synthesis of Metallic Glass Nanoparticles with Expanded Composition Space.

Nanoscale metallic glasses offer opportunities for investigating fundamental properties of amorphous solids and technological applications in biomedicine, microengineering, and catalysis. However, their top-down fabrication is limited by bulk counterpart availability, and bottom-up synthesis remains underexplored due to strict formation conditions. Here, a kinetically controlled flash carbothermic reaction is developed, featuring ultrafast heating (>105 K s-1) and cooling rates (>104 K s-1), for synthesizing metallic glass nanoparticles within milliseconds. Nine compositional permutations of noble metals, base metals, and metalloid (M1─M2─P, M1 = Pt/Pd, M2 = Cu/Ni/Fe/Co/Sn) are synthesized with widely tunable particle sizes and substrates. Through combinatorial development, a substantially expanded composition space for nanoscale metallic glass is discovered compared to bulk counterpart, revealing that the nanosize effect enhances glass forming ability. Leveraging this, several nanoscale metallic glasses are synthesized with composition that have never, to the knowledge, been synthesized in bulk. The metallic glass nanoparticles exhibit high activity in heterogeneous catalysis, outperforming crystalline metal alloy nanoparticles.

Enhancing the Electrode Gravimetric Capacity of Li1.2Mn0.4Ti0.4O2 Cathode Using Interfacial Carbon Deposition and Carbon Nanotube-Mediated Electrical Percolation.

Mn-based cation-disordered rocksalt oxides (Mn-DRX) are emerging as promising cathode materials for next-generation Li-ion batteries due to their high specific capacities and cobalt- and nickel-free characteristic. However, to reach the usable capacity, solid-state synthesized Mn-DRX materials require activation via postsynthetic ball milling, typically incorporating more than 20 wt % conductive carbon that adversely reduces the electrode-level gravimetric capacity. To address this issue, we first deposit amorphous carbon on the surface of the Li1.2Mn0.4Ti0.4O2 (LMTO) particles to increase the electrical conductivity by 5 orders of magnitude. Although the cathode material gravimetric first charge capacity reaches 180 mAh/g, its highly irreversible behavior leads to a first discharge capacity of 70 mAh/g. Subsequently, to ensure a good electrical percolation network, the LMTO material is ball-milled with a multiwall carbon nanotube (CNT) to obtain a 78.7 wt % LMTO active material loading in the cathode electrode (LMTO-CNT). As a result, a 210 mAh/g cathode electrode gravimetric first charge and 165 mAh/g first discharge capacity values are obtained, compared to the respective capacity values of 222 and 155 mAh/g for the LMTO material ball-milled with 20 wt % SuperP C65 electrode (LMTO-SP). After 50 cycles, LMTO-CNT delivers a 121 mAh/g electrode gravimetric discharge capacity, largely outperforming the value of 44 mAh/g of LMTO-SP. Our study demonstrates that while ball milling is necessary to achieve a significant amount of capacity of LMTO, a careful selection of additives, such as CNT, effectively reduces the required carbon quantity to achieve a higher electrode gravimetric discharge capacity.

Flash Recycling of Graphite Anodes.

The ever-increasing production of commercial lithium-ion batteries (LIBs) will result in a staggering accumulation of waste when they reach their end of life. A closed-loop solution, with effective recycling of spent LIBs, will lessen both the environmental impacts and economic cost of their use. Presently, <5% of spent LIBs are recycled and the regeneration of graphite anodes has, unfortunately, been mostly overlooked despite the considerable cost of battery-grade graphite. Here, an ultrafast flash recycling method to regenerate the graphite anode is developed and valuable battery metal resources are recovered. Selective Joule heating is applied for only seconds to efficiently decompose the resistive impurities. The generated inorganic salts, including lithium, cobalt, nickel, and manganese, can be easily recollected from the flashed anode waste using diluted acid, specifically 0.1 m HCl. The flash-recycled anode preserves the graphite structure and is coated with a solid-electrolyte-interphase-derived carbon shell, contributing to high initial specific capacity, superior rate performance, and cycling stability, when compared to anode materials recycled using a high-temperature-calcination method. Life-cycle-analysis relative to current graphite production and recycling methods indicate that flash recycling can significantly reduce the total energy consumption and greenhouse gas emission while turning anode recycling into an economically advantageous process.

Tunable Hybridized Morphologies Obtained through Flash Joule Heating of Carbon Nanotubes.

Hybrid carbon nanomaterials, such as those that incorporate carbon nanotubes into graphene sheets, have been found to display interesting mechanical and electrical properties because of their covalent bonding and π-π stacking domains. However, synthesis of these hybrid materials is limited by the high energetic cost of techniques like chemical vapor deposition. Here, we demonstrate the solvent- and gas-free synthesis of a 2D carbon nanotube/graphene network through flash Joule heating of pristine carbon nanotubes. The relative proportion of each morphology in the hybrid material can be tuned by varying the pulse time, as confirmed by Raman spectroscopy and microscopy. Triboindentation of epoxy composites made with the hybrid material shows increases of 162% and 64% to the hardness and Young's modulus, respectively, compared with the neat epoxy. These results demonstrate that flash Joule heating can be used to inexpensively convert carbon nanotubes into a hybrid network of nanotubes and graphene for use as an effective reinforcing additive in epoxy composites.

Upcycling of Waste Plastic into Hybrid Carbon Nanomaterials.

Graphitic 1D and hybrid nanomaterials represent a powerful solution in composite and electronic applications due to exceptional properties, but large-scale synthesis of hybrid materials has yet to be realized. Here, a rapid, scalable method to produce graphitic 1D materials from polymers using flash Joule heating (FJH) is reported. This avoids lengthy chemical vapor deposition and uses no solvent or water. The flash 1D materials (F1DM), synthesized using a variety of earth-abundant catalysts, have controllable diameters and morphologies by parameter tuning. Furthermore, the process can be modified to form hybrid materials, with F1DM bonded to turbostratic graphene. In nanocomposites, F1DM outperform commercially available carbon nanotubes. Compared to current 1D material synthetic strategies using life cycle assessment, FJH synthesis represents an 86-92% decrease in cumulative energy demand and 92-94% decrease in global-warming potential. This work suggests that FJH affords a cost-effective and sustainable route to upcycle waste plastic into valuable 1D and hybrid nanomaterials.

Synthesis of Clean Hydrogen Gas from Waste Plastic at Zero Net Cost.

Hydrogen gas (H2 ) is the primary storable fuel for pollution-free energy production, with over 90 million tonnes used globally per year. More than 95% of H2 is synthesized through metal-catalyzed steam methane reforming that produces 11 tonnes of carbon dioxide (CO2 ) per tonne H2 . "Green H2 " from water electrolysis using renewable energy evolves no CO2 , but costs 2-3× more, making it presently economically unviable. Here catalyst-free conversion of waste plastic into clean H2 along with high purity graphene is reported. The scalable procedure evolves no CO2 when deconstructing polyolefins and produces H2 in purities up to 94% at high mass yields. The sale of graphene byproduct at just 5% of its current value yields H2 production at a negative cost. Life-cycle assessment demonstrates a 39-84% reduction in emissions compared to other H2 production methods, suggesting the flash H2 process to be an economically viable, clean H2 production route.

Battery metal recycling by flash Joule heating.

The staggering accumulation of end-of-life lithium-ion batteries (LIBs) and the growing scarcity of battery metal sources have triggered an urgent call for an effective recycling strategy. However, it is challenging to reclaim these metals with both high efficiency and low environmental footprint. We use here a pulsed dc flash Joule heating (FJH) strategy that heats the black mass, the combined anode and cathode, to >2100 kelvin within seconds, leading to ~1000-fold increase in subsequent leaching kinetics. There are high recovery yields of all the battery metals, regardless of their chemistries, using even diluted acids like 0.01 M HCl, thereby lessening the secondary waste stream. The ultrafast high temperature achieves thermal decomposition of the passivated solid electrolyte interphase and valence state reduction of the hard-to-dissolve metal compounds while mitigating diffusional loss of volatile metals. Life cycle analysis versus present recycling methods shows that FJH significantly reduces the environmental footprint of spent LIB processing while turning it into an economically attractive process.

Holey and Wrinkled Flash Graphene from Mixed Plastic Waste.

High surface area varieties of graphene have captured significant attention, allowing for improved performance in a variety of applications. However, there are challenges facing the use of graphene in these applications since it is expensive and difficult to synthesize in bulk. Here, we leverage the capabilities of flash Joule heating to synthesize holey and wrinkled flash graphene (HWFG) in seconds from mixed plastic waste feedstocks, using in situ salt decomposition to produce and stabilize pore formation during the reaction. Surface areas as high as 874 m2 g-1 are obtained, with characteristics of micro-, meso-, and macroporosities. Raman spectroscopy confirms the wrinkled and turbostratic nature of the HWFG. We demonstrate HWFG applications in its use as a metal-free hydrogen evolution reaction electrocatalyst, with excellent stability, competitive overpotential, and Tafel slope; in a Li-metal battery anode allowing for stable and high discharge rates; and in a material with high gas adsorption. This represents an upcycle of mixed plastic waste, thereby affording a valuable route to address this pressing environmental pollutant concern.

Case Report: DARS Mutations Responsible for Hypomyelination With Brain Stem and Spinal Cord Involvement and Leg Spasticity.

Objective: Hypomyelination with brain stem and spinal cord involvement and leg spasticity (HBSL) is a rare form of leukodystrophy presenting with varying clinical and imaging features. We report a case of HBSL to investigate the clinical and radiological characteristics of HBSL resulting from cytoplasmic aspartyl-tRNA synthetase gene (DARS) mutations. Subjects: We report a patient of HBSL with compound heterozygous mutations in DARS1. To study the potential genetic variations of the patient, targeted next-generation sequencing, whole-exome sequencing, and Sanger sequencing were used. We reviewed the clinical and radiological features of the patient. The literature was thoroughly evaluated. Results: The patient suffered from developmental regression associated with lower limbs spasticity, developmental delay, and paralysis of the lower limbs since childhood. Decreased T1 and increased T2 signals were observed on the bilateral basal, centrum ovale, frontal lobe, parietal lobe, and ganglia in cervical cord magnetic resonance imaging (MRI). The patient had two compound heterozygous mutations (NM_001349:c.1363T > C and NM_001349:c.821C > G) in the DARS1 gene. Conclusion: Two mutations in DARS1 were found to be associated with HBSL, one of them being reported for the first time. These findings can be valuable for diagnosing and providing genetic counseling to HBSL patients in the future.

Plastic Waste Product Captures Carbon Dioxide in Nanometer Pores.

Plastic waste (PW) and increasing atmospheric carbon dioxide (CO2) levels are among the top environmental concerns presently facing humankind. With an ambitious 2050 zero-CO2 emissions goal, there is a demand for economical CO2 capture routes. Here we show that the thermal treatment of PW in the presence of potassium acetate yields an effective carbon sorbent with pores width of 0.7-1.4 nm for CO2 capture. The PW to carbon sorbent process works with single or mixed streams of polyolefin plastics. The CO2 capacity of the sorbent at 25 °C is 17.0 ± 1.1 wt % (3.80 ± 0.25 mmol g-1) at 1 bar and 5.0 ± 0.6 wt % (1.13 ± 0.13 mmol g-1) at 0.15 bar, and it regenerates upon reaching 75 ± 5 °C. The CO2 capture cost from flue gas via this technology is estimated to be <$21 ton-1 CO2, much lower than competing CO2 capture technologies. Hence, this PW-derived carbon material should find utility in the capture of CO2 from point sources of high CO2 emissions while providing a use for otherwise deleterious PW.

Robust Superhydrophobic Surfaces via the Sand-In Method.

Superhydrophobic surfaces have gained sustained attention because of their extensive applications in the fields of self-cleaning, anti-icing, and drag reduction systems. Water droplets must have large apparent contact angle (CA) (>150°) and small CA hysteresis (<10°) on these surfaces. However, previous research usually involves complex fabrication strategies to modify the surface wettability. It is also challenging to maintain the temporal and mechanical stability of the delicate surface textures. Here, we develop a one-step solvent-free sand-in method to fabricate robust superhydrophobic surfaces directly atop various substrates with an apparent CA up to ∼163.8° and hysteresis less than 5°. The water repellency can withstand 100 Scotch tape peeling tests and remain stable after being stored under ambient humid conditions in Houston, Texas, for 18 months or being heated at 130 °C in air for 24 h. The superhydrophobic surfaces have excellent anti-icing ability, including a ∼2.6× longer water freezing time and ∼40% smaller ice adhesion strength with the temperature as low as -35 °C. Since the surface layers are fabricated by sanding the substrates with the powder additives, the surface damage can be repaired by a direct re-sanding treatment with the same powder additives. Further sand-in condition screenings broaden surface wettability from hydrophilic to superhydrophobic. The sand-in method induces the surface modification and the formation of the tribofilm. Surface and materials characterizations reveal that both microstructures and nanoscale asperities of the tribofilms contribute to the robust superhydrophobic features of sanded surfaces.