Shape-transformable liquid metal nanoparticles in aqueous solution.
ABSTRACT: Stable suspensions of eutectic gallium indium (EGaIn) liquid metal nanoparticles form by probe-sonicating the metal in an aqueous solution. Positively-charged molecular or macromolecular surfactants in the solution, such as cetrimonium bromide or lysozyme, respectively, stabilize the suspension by interacting with the negative charges of the surface oxide that forms on the metal. The liquid metal breaks up into nanospheres via sonication, yet can transform into rods of gallium oxide monohydroxide (GaOOH) via moderate heating in solution either during or after sonication. Whereas heating typically drives phase transitions from solid to liquid (via melting), here heating drives the transformation of particles from liquid to solid via oxidation. Interestingly, indium nanoparticles form during the process of shape transformation due to the selective removal of gallium. This dealloying provides a mechanism to create indium nanoparticles at temperatures well below the melting point of indium. To demonstrate the versatility, we show that it is possible to shape transform and dealloy other alloys of gallium including ternary liquid metal alloys. Scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS) mapping, and X-ray diffraction (XRD) confirm the dealloying and transformation mechanism.
Project description:Liquid metals have attracted attention as functional components for moldable electronics, such as soft flexible connectors, wires or conductive ink. The relatively high surface tension (>?400 mN m<sup>-1</sup>) and the fact that liquid metals do not readily wet ceramic or oxide surfaces have led to devising unique techniques to spread the liquid and mold its shape. These techniques include surface modification, electrowetting and vacuum filling of channels. This work presents an injection technique based on pressurized fountain pen lithography with glass nanopipettes developed to directly pattern liquid metal on flat hard substrates. The liquid metals were eutectic alloys of Gallium, including Gallium-Indium (EGaIn), Gallium-Indium-Zinc and Gallium-Indium-Tin. The nanopipettes were coated internally with gold, acting as a sacrificial layer and facilitating the wetting of the pipette down to its pore, with an inner diameter of?~?100-300 nm. By applying hydrodynamic pressure to the connected end of the pipette, the metal was extruded through the pore, forming long continuous (>?3 mm) and narrow (~?1-15 µm) metal lines on silicon oxide and gold surfaces at room temperature and ambient conditions. With this robust platform, it is possible to pattern liquid metals on a variety of substrates and geometries down to the micron range.
Project description:Owing to their intrinsic properties, such as deformability, high electrical conductivity, and superior electrochemical performance, room-temperature liquid metals and liquid metal alloys have attracted the attention of researchers for a wide variety of applications, including portable and large-scale energy storage applications. In this study, novel gallium-indium-tin eutectic (EGaInSn) room-temperature liquid metal nanoparticles synthesized using a facile and scalable probe-ultrasonication method were used as anode material in lithium-ion batteries. The morphology, geometry, and self-healing properties of the synthesized room-temperature liquid metal nanoparticles were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (SEM/EDS and TEM/EDS). The synthesized room-temperature liquid metal nanoparticles delivered a specific capacity of 474 mAh g<sup>-1</sup> and retained 77% of the stable reversible capacity after 500 galvanostatic charge-discharge cycles at a constant current density of 0.1 A g<sup>-1</sup>. The high theoretical specific capacity, combined with its self-healing and fluidic features, make EGaInSn room-temperature liquid metal nanoparticles a potential anode material for large-scale energy storage applications.
Project description:To date, numerous inorganic nanocarriers have been explored for drug delivery systems (DDSs). However, the clinical application of inorganic formulations has often been hindered by their toxicity and failure to biodegrade. We describe here a transformable liquid-metal nanomedicine, based on a core-shell nanosphere composed of a liquid-phase eutectic gallium-indium core and a thiolated polymeric shell. This formulation can be simply produced through a sonication-mediated method with bioconjugation flexibility. The resulting nanoparticles loaded with doxorubicin (Dox) have an average diameter of 107?nm and demonstrate the capability to fuse and subsequently degrade under a mildly acidic condition, which facilitates release of Dox in acidic endosomes after cellular internalization. Equipped with hyaluronic acid, a tumour-targeting ligand, this formulation displays enhanced chemotherapeutic inhibition towards the xenograft tumour-bearing mice. This liquid metal-based DDS with fusible and degradable behaviour under physiological conditions provides a new strategy for engineering theranostic agents with low toxicity.
Project description:With tremendous research advances in biomedical application, liquid metals (LM) also offer fantastic chemistry for synthesis of novel nano-composites. Herein, as a pioneering trial, litchi-shaped heterogeneous eutectic gallium indium-Au nanoparticles (EGaIn-Au NPs), served as effective radiosensitizer and photothermal agent for radio-photothermal cancer therapy, have been successfully prepared using in situ interfacial galvanic replacement reaction. The enhanced photothermal conversion efficiency and boosted radio-sensitization effect could be achieved with the reduction of Au nanodots onto the eutectic gallium indium (EGaIn) NPs surface. Most importantly, the growth of tumor could be effectively inhibited under the combined radio-photothermal therapy mediated by EGaIn-Au NPs. Inspired by this approach, in situ interfacial galvanic replacement reaction may open a novel strategy to fabricate LM-based nano-composite with advanced multi-functionalities. Graphical abstract Image 1 Highlights • A facile method to synthesize heterogeneous liquid metal-Au nano-composite.• The galvanic replacement reaction mechanism is proposed for the first time.• The in situ growth of Au nanodots can improve radio-photothermal effect.• The enhanced radio-photothermal effect can effectively achieve cancer therapy.
Project description:Although Raney nickel made by dealloying has been used as a heterogeneous catalyst in a variety of organic syntheses for more than 80 years, only recently scientists have begun to realize that dealloying can generate nanoporous alloys with extraordinary structural characteristics. Herein, we achieved successful synthesis of a variety of monodisperse alloy nanoporous nanoparticles via a facile chemical dealloying process using nanocrystalline alloys as precursors. The as-prepared alloy nanoporous nanoparticles with large surface area and small pores show superior catalytic properties compared with alloyed nanoparticles. It is believed that these novel alloy nanoporous nanoparticles would open up new opportunities for catalytic applications.
Project description:Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide "skin" enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects.
Project description:Three-dimensional bicontinuous open (3DBO) nanoporosity has been recognized as an important nanoarchitecture for catalysis, sensing, and energy storage. Dealloying, i.e., selectively removing a component from an alloy, is an efficient way to fabricate nanoporous materials. However, current electrochemical and liquid-metal dealloying methods can only be applied to a limited number of alloys and usually require an etching process with chemical waste. Here, we report a green and universal approach, vapor-phase dealloying, to fabricate nanoporous materials by utilizing the vapor pressure difference between constituent elements in an alloy to selectively remove a component with a high partial vapor pressure for 3DBO nanoporosity. We demonstrate that extensive elements, regardless of chemical activity, can be fabricated as nanoporous materials with tunable pore sizes. Importantly, the evaporated components can be fully recovered. This environmentally friendly dealloying method paves a way to fabricate 3DBO nanoporous materials for a wide range of structural and functional applications.
Project description:Platinum-based alloys with low cost transition metals have been considered as promising electrocatalysts in the field of sustainable energy conversion and storage. Herein, chloroplatinic acid, cobalt chloride, and carbon nanotubes are used as platinum, cobalt precursors, and carriers, respectively, to prepare rich Pt dealloying PtCo nanoparticles (SD-PtCo/CNT) via co-liquid phase reduction and chemical dealloying methods. The characterization and test results confirm that PtCo alloy nanoparticles are evenly dispersed on carbon nanotubes, further dealloying and resulting in the partial dissolving of cobalt, simultaneously generating a rich Pt layer and roughly active surface. Benefiting from the unique structure, the SD-PtCo/CNT catalyst displays obviously enhanced HER activity in both acidic and alkaline conditions. In 1.0 M KOH, SD-PtCo/CNT exhibits a low overpotential of 78 mV at 10 mA/cm2 and a small tafel slope (38.28 mV/dec). In 0.5 M H2SO4, SD-PtCo/CNT still shows the superior performance compared with un-dealloying PtCo/CNT, with an overpotential of 17 mV at 10 mA/cm2 and corresponding tafel slope of 21.35 mV/dec. The high HER activity of SD-PtCo/CNT can be attributed to the formation of a platinum rich layer and the uniformly dispersed PtCo nanoparticles supported on superior conductive carbon nanotubes, suggesting its great potential for hydrogen generation via water splitting.
Project description:The development of non-noble nano-porous metal materials is hindered by surface oxidation reactions and from the difficulty to generate long range order pore arrays. Dealloying is a promising route to generate such materials by selective chemical etching of metal alloy materials. This process can generate nano-metal materials with superior plasmonic, catalytic and adsorptive surface properties. Here, the impact of properties of the etching solution on the dealloying process to generate nano-pores across thin film alloys was investigated by in-situ SAXS dealloying experiments. Single phase CuZn alloys were used as model materials to evaluate the influence of the solution temperature on the pore formation kinetics. This novel analysis allowed to visualize the change in surface properties of the materials over time, including their surface area as well as their pore and ligament sizes. The dealloying kinetics at the very early stage of the process were found to be critical to both stable pore formation and stabilization. SAXS in-situ data were correlated to the morphological properties of the materials obtained from ex-situ samples by Rutherford back scattering and scanning electron microscopy.
Project description:Gallium-based liquid metal can be used as a material for microheaters because it can be easily filled into microchannels and electrified to generate Joule heat, but the liquid metal-based microheater will suffer breakage induced by voids forming within the liquid metal when the temperature normally gets higher than 100 °C. To resolve this problem, a novel liquid metal-based microheater with parallel ventilating side-channels is presented. It consists of a liquid-metal heating channel and two parallel ventilating side-channels. The heating channel is connected with the side-channels by small gaps between polydimethylsiloxane (PDMS) posts. Experimental results show that this novel microheater can be heated up to 200 °C without damage. To explain its excellent performance, an experiment is performed to discover the development of the voids within the liquid-metal heating channel, and two reasons are put forward in this work on the basis of the experiment. Afterward pressing and bending tests are conducted to explore the mechanical stability of the novel microheaters. Finally, the microheaters are applied to warm water to show their good flexibility on non-flat surfaces. In consequence, the novel liquid metal-based microheater is believed to be widely applicable to soft micro-electro-mechanical system(MEMS) heating devices.