Project description:Polymer-metal nanocomposites are of increasing interest for a wide range of applications; however, the preparation of these nanocomposites often requires the addition of external initiation and reducing agents for the synthesis of polymer and metal nanoparticles, respectively. Herein, we demonstrate the preparation of polymer-metal nanocomposites for improved catalytic performance by utilizing ultrasound as both the initiation and reducing source. Specifically, synthesis of the macro-RAFT agent containing poly[2-(dimethylamino)ethyl methacrylate], followed by ultrasound-initiated polymerization-induced self-assembly (sono-PISA), provides triblock copolymer nanoparticles containing tertiary amine groups. These polymer nanoparticles were further used as the scaffold for the in situ reduction of metal ions (Au and Pd ions) by radicals generated via sonolysis of water without additional reducing agents. The immobilization of metal nanoparticles has been confirmed by TEM and electron diffraction patterns. Polymer-Au nanocomposites with stepwise-grown AuNPs can be applied as surface-enhanced Raman scattering (SERS) substrates for 4-aminothiophenol (4-ATP) detection. Furthermore, the catalytic performances of these prepared polymer-Au and polymer-Pd nanocomposites were examined for aerobic alcohol oxidation and the Suzuki-Miyaura cross-coupling reaction, respectively. Overall, this strategy is expected to greatly expand the utility of ultrasound in the preparation of polymer-metal nanocomposites and promote the catalytic applications of these nanocomposites.
Project description:Hydrogen (H2) sensors that can be produced en masse with cost-effective manufacturing tools are critical for enabling safety in the emerging hydrogen economy. The use of melt-processed nanocomposites in this context would allow the combination of the advantages of plasmonic hydrogen detection with polymer technology; an approach which is held back by the slow diffusion of H2 through the polymer matrix. Here, we show that the use of an amorphous fluorinated polymer, compounded with colloidal Pd nanoparticles prepared by highly scalable continuous flow synthesis, results in nanocomposites that display a high H2 diffusion coefficient in the order of 10-5 cm2 s-1. As a result, plasmonic optical hydrogen detection with melt-pressed fluorinated polymer nanocomposites is no longer limited by the diffusion of the H2 analyte to the Pd nanoparticle transducer elements, despite a thickness of up to 100 μm, thereby enabling response times as short as 2.5 s at 100 mbar (≡10 vol. %) H2. Evidently, plasmonic sensors with a fast response time can be fabricated with thick, melt-processed nanocomposites, which paves the way for a new generation of robust H2 sensors.
Project description:Stretchable, biocompatible devices can bridge electronics and biology. However, most stretchable conductors for such devices are toxic, costly, and regularly break/degrade after several large deformations. Here we show printable, highly stretchable, and biocompatible metal-polymer conductors by casting and peeling off polymers from patterned liquid metal particles, forming surface-embedded metal in polymeric hosts. Our printable conductors present good stretchability (2,316 S/cm at a strain of 500%) and repeatability (ΔR/R <3% after 10,000 cycles), which can satisfy most electrical applications in extreme deformations. This strategy not only overcomes large surface tension of liquid metal but also avoids the undesirable sintering of its particles by stress in deformations, such that stretchable conductors can form on various substrates with high resolution (15 μm), high throughput (∼2,000 samples/hour), and low cost (one-quarter price of silver). We use these conductors for stretchable circuits, motion sensors, wearable glove keyboards, and electroporation of live cells.
Project description:Heat dissipation materials in which fillers are dispersed in a polymer matrix typically do not exhibit both high thermal conductivity (k) and processability due to a trade-off. In this paper, we fabricate heat dissipation composites which overcome the trade-off using liquid metal (LM). By exceeding the conventional filler limit, ten times higher k is achieved for a 90 vol% LM composite compared with k of 50 vol% LM composite. Further, an even higher k is achieved by introducing h-BN between the LM droplets, and the highest k in this study was 17.1 W m-1 K-1. The LM composite is processable at room temperature and used as inks for 3D printing. This combination of high k and processability not only allows heat dissipation materials to be processed on demand under ambient conditions but it also increases the surface area of the LM composite, which enables rapid heat dissipation.
Project description:Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD+ to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal-polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD+ reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity.
Project description:We here demonstrate the preparation of composite polymer electrolytes (CPEs) for Li-ion batteries, applicable for 3D printing process via fused deposition modeling. The prepared composites consist of modified poly(ethylene glycol) (PEG), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and SiO2-based nanofillers. PEG was successfully end group modified yielding telechelic PEG containing either ureidopyrimidone (UPy) or barbiturate moieties, capable to form supramolecular networks via hydrogen bonds, thus introducing self-healing to the electrolyte system. Silica nanoparticles (NPs) were used as a filler for further adjustment of mechanical properties of the electrolyte to enable 3D-printability. The surface functionalization of the NPs with either ionic liquid (IL) or hydrophobic alkyl chains is expected to lead to an improved dispersion of the NPs within the polymer matrix. Composites with different content of NPs (5%, 10%, 15%) and LiTFSI salt (EO/Li+ = 5, 10, 20) were analyzed via rheology for a better understanding of 3D printability, and via Broadband Dielectric Spectroscopy (BDS) for checking their ionic conductivity. The composite electrolyte PEG 1500 UPy2/LiTFSI (EO:Li 5:1) mixed with 15% NP-IL was successfully 3D printed, revealing its suitability for application as printable composite electrolytes.
Project description:A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm(2). To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per ?m(2). This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings.
Project description:A range of protic ionic liquids (PILs) based on tri-n-alkylammonium cations and mesylate/triflate anions were incorporated into a polymer matrix to form ionogels (IGs). These systems were investigated for their thermal and electrochemical behaviour, as well as under the aspect of ion motion via PFG-NMR. The ionic conductivities of the ILs/IGs are in the range of 10-4-10-3 S/cm-1 at elevated temperatures and the diffusion coefficients are around 10-11 m2 s-1. Successful 3D printing of an IG with 70 wt % of IL is possible via stereolithography approaches, opening up applications in, e. g., structured ion-conductive membranes.
Project description:Background: Nanotechnology, even if unknowingly, has been used for millennia. The occurrence of shiny colors in pottery and glass made hundreds and thousand of years ago is due to the presence of nanoparticles in the fabrication of such ornaments. In the last decade, 3D printing has revolutionized fabrication and manufacturing processes, making it easier to produce, in a simple and fast way, 3D objects. Results: In this paper we show how to fabricate a 3D-printable nanocomposite composed of dichroic gold nanoparticles and a 3D-printable polymer. The minute amount of gold nanoparticles used for obtaining the dichroic effect does not influence the mechanical properties of the polymer nor its printability. Thus, the nanocomposite can be easily 3D-printed using a standard 3D printer and shows a purple color in transmission and a brownish color in reflection. Conclusion: This methodology can be used not only by artists, but also for studying the optical properties of nanoparticles or, for example, for the 3D fabrication of optical filters.
Project description:Optical encryption technologies based on room-temperature light-emitting materials are of considerable interest. Herein, we present three-dimensional (3D) printable dual-light-emitting materials for high-performance optical pattern encryption. These are based on fluorescent perovskite nanocrystals (NCs) embedded in metal-organic frameworks (MOFs) designed for phosphorescent host-guest interactions. Notably, perovskite-containing MOFs emit a highly efficient blue phosphorescence, and perovskite NCs embedded in the MOFs emit characteristic green or red fluorescence under ultraviolet (UV) irradiation. Such dual-light-emitting MOFs with independent fluorescence and phosphorescence emissions are employed in pochoir pattern encryption, wherein actual information with transient phosphorescence is efficiently concealed behind fake information with fluorescence under UV exposure. Moreover, a 3D cubic skeleton is developed with the dual-light-emitting MOF powder dispersed in 3D-printable polymer filaments for 3D dual-pattern encryption. This article outlines a universal principle for developing MOF-based room-temperature multi-light-emitting materials and a strategy for multidimensional information encryption with enhanced capacity and security.