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.

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.

Turbostratic Boron-Carbon-Nitrogen and Boron Nitride by Flash Joule Heating.

Turbostratic layers in 2D materials have an interlayer misalignment. The lack of alignment expands the intrinsic interlayer distances and weakens the optical and electronic interactions between adjacent layers. This introduces properties distinct from those structures with well-aligned lattices and strong coupling interactions. However, direct and rapid synthesis of turbostratic materials remains a challenge owing to their thermodynamically metastable properties. Here, a flash Joule heating (FJH) method to achieve bulk synthesis of boron-carbon-nitrogen ternary compounds with turbostratic structures by a kinetically controlled ultrafast cooling process that takes place within milliseconds (103  to 104 K s-1 ) is reported. Theoretical calculations support the existence of turbostratic structures and provide estimates of the energy barriers with respect to conversion into the corresponding well-aligned counterparts. When using non-carbon conductive additives, a direct synthesis of boron nitride is possible. The turbostratic nature facilitates mechanical exfoliation and more stable dispersions. Accordingly, the addition of flash products to a poly(vinyl alcohol) nanocomposite film coating a copper surface greatly improves the copper's resistance to corrosion in 0.5 m sulfuric acid or 3.5 wt% saline solution. FJH allows the use of bulk materials as reactants and provides a rapid approach to large quantities of the hitherto hard-to-access turbostratic materials.

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.

Ultrafast and Controllable Phase Evolution by Flash Joule Heating.

Flash Joule heating (FJH), an advanced material synthesis technique, has been used for the production of high-quality carbon materials. Direct current discharge through the precursors by large capacitors has successfully converted carbon-based starting materials into bulk quantities of turbostratic graphene by the FJH process. However, the formation of other carbon allotropes, such as nanodiamonds and concentric carbon materials, as well as the covalent functionalization of different carbon allotropes by the FJH process, remains challenging. Here, we report the solvent-free FJH synthesis of three different fluorinated carbon allotropes: fluorinated nanodiamonds, fluorinated turbostratic graphene, and fluorinated concentric carbon. This is done by millisecond flashing of organic fluorine compounds and fluoride precursors. Spectroscopic analysis confirms the modification of the electronic states and the existence of various short-range and long-range orders in the different fluorinated carbon allotropes. The flash-time-dependent relationship is further demonstrated to control the phase evolution and product compositions.

Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating.

Controllable phase engineering is vital for precisely tailoring material properties since different phase structures have various electronic states and atomic arrangements. Rapid synthesis of thermodynamically metastable materials, especially two-dimensional metastable materials, with high efficiency and low cost remains a large challenge. Here we report flash Joule heating (FJH) as an electrothermal method to achieve the bulk conversion of transition metal dichalcogenides, MoS2 and WS2, from 2H phases to 1T phases in milliseconds. The conversions can reach up to 76% of flash MoS2 using tungsten powder as conductive additive. Different degrees of phase conversion can be realized by controlling the FJH conditions, such as reaction duration and additives, which allows the study of ratio-dependent properties. First-principles calculations confirm that structural processes associated with the FJH, such as vacancy formation and charge accumulation, result in stabilization of the 1T phases. FJH offers rapid access to bulk quantities of the hitherto hard-to-access 1T phases, a promising method for further fundamental research and diverse applications of metastable phases.

Flash Graphene from Plastic Waste.

In this work, an approach to upcycling plastic waste (PW) products is presented. The method relies on flash Joule heating (FJH) to convert PW into flash graphene (FG). In addition to FG, the process results in the formation of carbon oligomers, hydrogen, and light hydrocarbons. In order to make high-quality graphene, a sequential alternating current (AC) and direct current (DC) flash is used. The FJH process requires no catalyst and works for PW mixtures, which makes the process suitable for handling landfill PW. The energy required to convert PW to FG is ∼23 kJ/g or ∼$125 in electricity per ton of PW, potentially making this process economically attractive for scale-up. The FG was characterized by Raman spectroscopy and had an I2D/IG peak ratio up to 6 with a low-intensity D band. Moreover, transmission electron microscopy and X-ray diffraction analysis show that the FG is turbostratic with an interlayer spacing of 3.45 Å. The large interlayer spacing will facilitate its dispersion in liquids and composites. Analysis of FG dispersions in 1% Pluronic aqueous solution shows that concentrations up to 1.2 mg/mL can be achieved. The carbon oligomers that distilled from the process were characterized by Fourier transform infrared spectroscopy and have chemical structures similar to the starting PW. Initial analysis of gas-phase products shows the formation of considerable amounts of hydrogen along with other light hydrocarbons. As graphene is naturally occurring and shows a low toxicity profile, this could be an environmentally beneficial method to upcycle PW.

Flash Graphene Morphologies.

Flash Joule heating (FJH) can convert almost any carbon-based precursor into bulk quantities of graphene. This work explores the morphologies and properties of flash graphene (FG) generated from carbon black. It is shown that FG is partially comprised of sheets of turbostratic FG (tFG) that have a rotational mismatch between neighboring layers. The remainder of the FG is wrinkled graphene sheets that resemble nongraphitizing carbon. To generate high quality tFG sheets, a FJH duration of 30-100 ms is employed. Beyond 100 ms, the turbostratic sheets have time to AB-stack and form bulk graphite. Atomistic simulations reveal that generic thermal annealing yields predominantly wrinkled graphene which displays minimal to no alignment of graphitic planes, as opposed to the high-quality tFG that might be formed under the direct influence of current conducted through the material. The tFG was easily exfoliated via shear, hence the FJH process has the potential for bulk production of tFG without the need for pre-exfoliation using chemicals or high energy mechanical shear.