Some things seem small...
Yet are extraordinarily strong!
Robust Superhydrophobic Surfaces via the Sand-In Method.
ACS applied materials & interfaces
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.
View details for DOI 10.1021/acsami.2c05076
View details for PubMedID 35862236
Turbostratic Boron-Carbon-Nitrogen and Boron-Nitride by Flash Joule Heating.
Advanced materials (Deerfield Beach, Fla.)
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, we report 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 (103 104 K s-1 ). 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 polyvinyl 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. This article is protected by copyright. All rights reserved.
View details for DOI 10.1002/adma.202202666
View details for PubMedID 35748868
Brushed Metals for Rechargeable Metal Batteries.
Advanced materials (Deerfield Beach, Fla.)
Battery designs are swiftly changing from metal-ion to rechargeable metal batteries. Theoretically, metals can deliver maximum anode capacity and enable cells with improved energy density. In practice, these advantages are only possible if the parasitic surface reactions associated with metal anodes are controlled. These undesirable surface reactions are responsible for many troublesome issues, like dendrite formation and accelerated consumption of active materials, which leads to anodes with low cycle life or even battery runaway. Here, we report a facile and solvent-free brushing method to convert powders into films atop Li and Na metal foils. Benefiting from the reactivity of Li metal with these powder films, surface energy can be effectively tuned, thereby preventing parasitic reaction. In-operando study of P2 S5 -Li anodes in liquid electrolyte cells reveals a smoother electrode contour and more uniform Li metal electrodeposition and dissolution behavior during cycling. The P2 S5 -Li anodes sustain ultralow polarization in symmetric cell for >4000 h, 8* longer than bare Li anodes. The capacity retention is 70% higher when P2 S5 -Li anodes are paired with a practical LiFePO4 cathode (3.2 mAh cm-2 ) after 340 cycles. Brush coating opens a promising avenue to fabricate large-scale artificial solid-electrolyte-interphase directly on metals without the need for organic solvent. This article is protected by copyright. All rights reserved.
View details for DOI 10.1002/adma.202202668
View details for PubMedID 35709635
Light-activated molecular machines are fast-acting broad-spectrum antibacterials that target the membrane.
2022; 8 (22): eabm2055
The increasing occurrence of antibiotic-resistant bacteria and the dwindling antibiotic research and development pipeline have created a pressing global health crisis. Here, we report the discovery of a distinctive antibacterial therapy that uses visible (405 nanometers) light-activated synthetic molecular machines (MMs) to kill Gram-negative and Gram-positive bacteria, including methicillin-resistant Staphylococcus aureus, in minutes, vastly outpacing conventional antibiotics. MMs also rapidly eliminate persister cells and established bacterial biofilms. The antibacterial mode of action of MMs involves physical disruption of the membrane. In addition, by permeabilizing the membrane, MMs at sublethal doses potentiate the action of conventional antibiotics. Repeated exposure to antibacterial MMs is not accompanied by resistance development. Finally, therapeutic doses of MMs mitigate mortality associated with bacterial infection in an in vivo model of burn wound infection. Visible light-activated MMs represent an unconventional antibacterial mode of action by mechanical disruption at the molecular scale, not existent in nature and to which resistance development is unlikely.
View details for DOI 10.1126/sciadv.abm2055
View details for PubMedID 35648847
Heteroatom-Doped Flash Graphene
2022; 16 (5): 6646-6656
Heteroatom doping can effectively tailor the local structures and electronic states of intrinsic two-dimensional materials, and endow them with modified optical, electrical, and mechanical properties. Recent studies have shown the feasibility of preparing doped graphene from graphene oxide and its derivatives via some post-treatments, including solid-state and solvothermal methods, but they require reactive and harsh reagents. However, direct synthesis of various heteroatom-doped graphene in larger quantities and high purity through bottom-up methods remains challenging. Here, we report catalyst-free and solvent-free direct synthesis of graphene doped with various heteroatoms in bulk via flash Joule heating (FJH). Seven types of heteroatom-doped flash graphene (FG) are synthesized through millisecond flashing, including single-element-doped FG (boron, nitrogen, oxygen, phosphorus, sulfur), two-element-co-doped FG (boron and nitrogen), as well as three-element-co-doped FG (boron, nitrogen, and sulfur). A variety of low-cost dopants, such as elements, oxides, and organic compounds are used. The graphene quality of heteroatom-doped FG is high, and similar to intrinsic FG, the material exhibits turbostraticity, increased interlayer spacing, and superior dispersibility. Electrochemical oxygen reduction reaction of different heteroatom-doped FG is tested, and sulfur-doped FG shows the best performance. Lithium metal battery tests demonstrate that nitrogen-doped FG exhibits a smaller nucleation overpotential compared to Cu or undoped FG. The electrical energy cost for the synthesis of heteroatom-doped FG synthesis is only 1.2 to 10.7 kJ g-1, which could render the FJH method suitable for low-cost mass production of heteroatom-doped graphene.
View details for DOI 10.1021/acsnano.2c01136
View details for Web of Science ID 000813129800001
View details for PubMedID 35320673
Machine Learning Guided Synthesis of Flash Graphene.
Advanced materials (Deerfield Beach, Fla.)
Advances in nanoscience have enabled the synthesis of nanomaterials, such as graphene, from low-value or waste materials through flash Joule heating. Though this capability is promising, the complex and entangled variables that govern nanocrystal formation in the Joule heating process remain poorly understood. In this work, we construct machine learning (ML) models to explore the factors that drive the transformation of amorphous carbon into graphene nanocrystals during flash Joule heating. An XGBoost regression model of crystallinity achieves an r2 score of 0.8051 ± 0.054. Feature importance assays and decision trees extracted from these models reveal key considerations in the selection of starting materials and the role of stochastic current fluctuations in flash Joule heating synthesis. Furthermore, partial dependence analyses demonstrate the importance of charge and current density as predictors of crystallinity, implying a progression from reaction-limited to diffusion-limited kinetics as flash Joule heating parameters change. Finally, we show a practical application of the ML models by using Bayesian meta-learning algorithms to automatically improve bulk crystallinity over many Joule heating reactions. These results illustrate the power of ML as a tool to analyze complex nanomanufacturing processes and enable the synthesis of 2D crystals with desirable properties by flash Joule heating. This article is protected by copyright. All rights reserved.
View details for DOI 10.1002/adma.202106506
View details for PubMedID 35064973
- Sounds of Synthesis: Acoustic Real-Time Analysis of Laser-Induced Graphene ADVANCED FUNCTIONAL MATERIALS 2022
Phase controlled synthesis of transition metal carbide nanocrystals by ultrafast flash Joule heating.
1800; 13 (1): 262
Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, Cr2C3, MoC, and W2C) and covalent carbides (B4C and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including beta-Mo2C and metastable alpha-MoC1-x and eta-MoC1-x are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000K coupled with kinetically controlled ultrafast cooling (>104Ks-1). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with beta-Mo2C showing the best performance.
View details for DOI 10.1038/s41467-021-27878-1
View details for PubMedID 35017518
Ultrafast and Controllable Phase Evolution by Flash Joule Heating
2021; 15 (7): 11158-11167
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.
View details for DOI 10.1021/acsnano.1c03536
View details for Web of Science ID 000679406500017
View details for PubMedID 34138536
High-Resolution Laser-Induced Graphene from Photoresist
2021; 15 (5): 8976-8983
The fabrication of patterned graphene electronics at high resolution is an important challenge for many applications in microelectronics. Here, we demonstrate the conversion of positive photoresist (PR), commonly employed in the commercial manufacture of consumer electronics, into laser-induced graphene (LIG). Sequential lasing converts the PR photopolymer first into amorphous carbon, then to photoresist-derived LIG (PR-LIG). The resulting material possesses good conductivity and is easily doped with metal or other additives for additional functionality. Furthermore, photolithographic exposure of PR prior to lasing enables the generation of PR-LIG patterns small enough to be invisible to the naked eye. By exploiting PR as a photopatternable LIG precursor, PR-LIG can be synthesized with a spatial resolution of ∼10 μm, up to 15 times smaller than conventional LIG patterning methods. The patterning of these small PR-LIG features could offer a powerful and broadly accessible strategy for the fabrication of microscale LIG-derived nanocomposites for on-chip devices.
View details for DOI 10.1021/acsnano.1c01843
View details for Web of Science ID 000656994100093
View details for PubMedID 33900723
Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating
2021; 15 (1): 1282-1290
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.
View details for DOI 10.1021/acsnano.0c08460
View details for Web of Science ID 000613942700099
View details for PubMedID 33412009
Nanocars with Permanent Dipoles: Preparing for the Second International Nanocar Race
JOURNAL OF ORGANIC CHEMISTRY
2020; 85 (21): 13644-13654
With the desire to synthesize surface-rolling molecular machines that can be translated and rotated with extreme precision and speed, we have synthesized a series of five nanocars. Each structure features a permanent dipole moment, generated by an N,N-dimethylamino- moiety on one end of the car coupled with a nitro group on the other end. These cars are designed to be stimulated with an electric field gradient from a scanning probe microscopy tip. The nanocars all possess unexplored combinations of structural features: tert-butyl wheels, short alkyne chassis, and combination sets of wheels including one set of tert-butyl wheels and another set of larger adamantane wheels on the same car. Each of these features needs to be assessed as preparation for the second International Nanocar Race that is taking place in 2022.
View details for DOI 10.1021/acs.joc.0c01811
View details for Web of Science ID 000589941700023
View details for PubMedID 33085894
Flash Graphene Morphologies
2020; 14 (10): 13691-13699
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.
View details for DOI 10.1021/acsnano.0c05900
View details for Web of Science ID 000586793400117
View details for PubMedID 32909736
Laminated Laser-Induced Graphene Composites
2020; 14 (7): 7911-7919
Laser-induced graphene (LIG) is a porous graphene foam generated by lasing carbon-based precursors. Compositing LIG expands the spectrum of applications for which the material may be used. Techniques for scale-up of LIG composites will be essential as the technology approaches commercialization. Roll-to-roll processing is of special interest, as precisely controlled patterning can be performed in conjunction with continuous formation of composites. Here, we demonstrate a simple lamination compositing method that is compatible with roll-to-roll processing and yields functional, patterned, and multilayered LIG composites with various thermoplastic films. Multiple lamination steps are used to encapsulate LIG within composites. We also demonstrate several applications for LIG that have been enabled by the lamination compositing technique. These include robust flexible electrodes generated through laminating copper foil strips into the LIG composite, LIG-based triboelectric nanogenerators to harvest waste mechanical energy, antimicrobial LIG composite bandages with varying hydrophobicity, and LIG puncture detectors.
View details for DOI 10.1021/acsnano.0c02835
View details for Web of Science ID 000557762800020
View details for PubMedID 32441916
Self-Sterilizing Laser-Induced Graphene Bacterial Air Filter
2019; 13 (10): 11912-11920
Nosocomial infections transmitted through airborne, droplet, aerosol, and particulate-transported modes pose substantial infection risks to patients and healthcare employees. In this study, we demonstrate a self-cleaning filter comprised of laser-induced graphene (LIG), a porous conductive graphene foam formed through photothermal conversion of a polyimide film by a commercial CO2 laser cutter. LIG was shown to capture particulates and bacteria. The bacteria cannot proliferate even when submerged in culture medium. Through a periodic Joule-heating mechanism, the filter readily reaches >300 °C. This destroys any microorganisms including bacteria, along with molecules that can cause adverse biological reactions and diseases. These molecules include pyrogens, allergens, exotoxins, endotoxins, mycotoxins, nucleic acids, and prions. Capitalizing on the high surface area and thermal stability of LIG, the utility of graphene for reduction of nosocomial infection in hospital settings is suggested.
View details for DOI 10.1021/acsnano.9b05983
View details for Web of Science ID 000492801600100
View details for PubMedID 31560513
Laser-Induced Graphene Triboelectric Nanogenerators
2019; 13 (6): 7166-7174
Triboelectric nanogenerators (TENGs) show exceptional promise for converting wasted mechanical energy into electrical energy. This study investigates the use of laser-induced graphene (LIG) composites as an exciting class of triboelectric materials in TENGs. Infrared laser irradiation is used to convert the surfaces of the two carbon sources, polyimide (PI) and cork, into LIG. This gives the bilayer composite films the high conductivity associated with LIG and the triboelectric properties of the carbon source. A LIG/PI composite is used to fabricate TENGs based on conductor-to-dielectric and metal-free dielectric-to-dielectric device geometries with open-circuit voltages >3.5 kV and peak power >8 mW. Additionally, a single sheet of PI is converted to a metal-free foldable TENG. The LIG is also embedded within a PDMS matrix to form a single-electrode LIG/PDMS composite TENG. This single-electrode TENG is highly flexible and stretchable and was used to generate power from mechanical contact with skin. The LIG composites present a class of triboelectric materials that can be made from naturally occurring and synthetic carbon sources.
View details for DOI 10.1021/acsnano.9b02596
View details for Web of Science ID 000473248300101
View details for PubMedID 31117382