Cellulose Nanofiber-Alginate Biotemplated Cobalt Composite Multifunctional Aerogels for Energy Storage Electrodes.

Tunable porous composite materials to control metal and metal oxide functionalization, conductivity, pore structure, electrolyte mass transport, mechanical strength, specific surface area, and magneto-responsiveness are critical for a broad range of energy storage, catalysis, and sensing applications. Biotemplated transition metal composite aerogels present a materials approach to address this need. To demonstrate a solution-based synthesis method to develop cobalt and cobalt oxide aerogels for high surface area multifunctional energy storage electrodes, carboxymethyl cellulose nanofibers (CNF) and alginate biopolymers were mixed to form hydrogels to serve as biotemplates for cobalt nanoparticle formation via the chemical reduction of cobalt salt solutions. The CNF-alginate mixture forms a physically entangled, interpenetrating hydrogel, combining the properties of both biopolymers for monolith shape and pore size control and abundant carboxyl groups that bind metal ions to facilitate biotemplating. The CNF-alginate hydrogels were equilibrated in CaCl2 and CoCl2 salt solutions for hydrogel ionic crosslinking and the prepositioning of transition metal ions, respectively. The salt equilibrated hydrogels were chemically reduced with NaBH4, rinsed, solvent exchanged in ethanol, and supercritically dried with CO2 to form aerogels with a specific surface area of 228 m2/g. The resulting aerogels were pyrolyzed in N2 gas and thermally annealed in air to form Co and Co3O4 porous composite electrodes, respectively. The multifunctional composite aerogel's mechanical, magnetic, and electrochemical functionality was characterized. The coercivity and specific magnetic saturation of the pyrolyzed aerogels were 312 Oe and 114 emu/gCo, respectively. The elastic moduli of the supercritically dried, pyrolyzed, and thermally oxidized aerogels were 0.58, 1.1, and 14.3 MPa, respectively. The electrochemical testing of the pyrolyzed and thermally oxidized aerogels in 1 M KOH resulted in specific capacitances of 650 F/g and 349 F/g, respectively. The rapidly synthesized, low-cost, hydrogel-based synthesis for tunable transition metal multifunctional composite aerogels is envisioned for a wide range of porous metal electrodes to address energy storage, catalysis, and sensing applications.

A Salt-Templated Synthesis Method for Porous Platinum-based Macrobeams and Macrotubes.

The synthesis of high surface area porous noble metal nanomaterials generally relies on time consuming coalescence of pre-formed nanoparticles, followed by rinsing and supercritical drying steps, often resulting in mechanically fragile materials. Here, a method to synthesize nanostructured porous platinum-based macrotubes and macrobeams with a square cross section from insoluble salt needle templates is presented. The combination of oppositely charged platinum, palladium, and copper square planar ions results in the rapid formation of insoluble salt needles. Depending on the stoichiometric ratio of metal ions present in the salt-template and the choice of chemical reducing agent, either macrotubes or macrobeams form with a porous nanostructure comprised of either fused nanoparticles or nanofibrils. Elemental composition of the macrotubes and macrobeams, determined with x-ray diffractometry and x-ray photoelectron spectroscopy, is controlled by the stoichiometric ratio of metal ions present in the salt-template. Macrotubes and macrobeams may be pressed into free standing films, and the electrochemically active surface area is determined with electrochemical impedance spectroscopy and cyclic voltammetry. This synthesis method demonstrates a simple, relatively fast approach to achieve high-surface area platinum-based macrotubes and macrobeams with tunable nanostructure and elemental composition that may be pressed into free-standing films with no required binding materials.

Synthesis Method for Cellulose Nanofiber Biotemplated Palladium Composite Aerogels.

Here, a method to synthesize cellulose nanofiber biotemplated palladium composite aerogels is presented. Noble metal aerogel synthesis methods often result in fragile aerogels with poor shape control. The use of carboxymethylated cellulose nanofibers (CNFs) to form a covalently bonded hydrogel allows for the reduction of metal ions such as palladium on the CNFs with control over both nanostructure and macroscopic aerogel monolith shape after supercritical drying. Crosslinking the carboxymethylated cellulose nanofibers is achieved using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) in the presence of ethylenediamine. The CNF hydrogels maintain their shape throughout synthesis steps including covalent crosslinking, equilibration with precursor ions, metal reduction with high concentration reducing agent, rinsing in water, ethanol solvent exchange, and CO2 supercritical drying. Varying the precursor palladium ion concentration allows for control over the metal content in the final aerogel composite through a direct ion chemical reduction rather than relying on the relatively slow coalescence of pre-formed nanoparticles used in other sol-gel techniques. With diffusion as the basis to introduce and remove chemical species into and out of the hydrogel, this method is suitable for smaller bulk geometries and thin films. Characterization of the cellulose nanofiber-palladium composite aerogels with scanning electron microscopy, X-ray diffractometry, thermal gravimetric analysis, nitrogen gas adsorption, electrochemical impedance spectroscopy, and cyclic voltammetry indicates a high surface area, metallized palladium porous structure.

Noble Metal Composite Porous Silk Fibroin Aerogel Fibers.

Nobel metal composite aerogel fibers made from flexible and porous biopolymers offer a wide range of applications, such as in catalysis and sensing, by functionalizing the nanostructure. However, producing these composite aerogels in a defined shape is challenging for many protein-based biopolymers, especially ones that are not fibrous proteins. Here, we present the synthesis of silk fibroin composite aerogel fibers up to 2 cm in length and a diameter of ~300 µm decorated with noble metal nanoparticles. Lyophilized silk fibroin dissolved in hexafluoro-2-propanol (HFIP) was cast in silicon tubes and physically crosslinked with ethanol to produce porous silk gels. Composite silk aerogel fibers with noble metals were created by equilibrating the gels in noble metal salt solutions reduced with sodium borohydride, followed by supercritical drying. These porous aerogel fibers provide a platform for incorporating noble metals into silk fibroin materials, while also providing a new method to produce porous silk fibers. Noble metal silk aerogel fibers can be used for biological sensing and energy storage applications.

Salt-Mediated Au-Cu Nanofoam and Au-Cu-Pd Porous Macrobeam Synthesis.

Multi-metallic and alloy nanomaterials enable a broad range of catalytic applications with high surface area and tuning reaction specificity through the variation of metal composition. The ability to synthesize these materials as three-dimensional nanostructures enables control of surface area, pore size and mass transfer properties, electronic conductivity, and ultimately device integration. Au-Cu nanomaterials offer tunable optical and catalytic properties at reduced material cost. The synthesis methods for Au-Cu nanostructures, especially three-dimensional materials, has been limited. Here, we present Au-Cu nanofoams and Au-Cu-Pd macrobeams synthesized from salt precursors. Salt precursors formed from the precipitation of square planar ions resulted in short- and long-range ordered crystals that, when reduced in solution, form nanofoams or macrobeams that can be dried or pressed into freestanding monoliths or films. Metal composition was determined with X-ray diffraction and energy dispersive X-ray spectroscopy. Nitrogen gas adsorption indicated an Au-Cu nanofoam specific surface area of 19.4 m²/g. Specific capacitance determined with electrochemical impedance spectroscopy was 46.0 F/g and 52.5 F/g for Au-Cu nanofoams and Au-Cu-Pd macrobeams, respectively. The use of salt precursors is envisioned as a synthesis route to numerous metal and multi-metallic nanostructures for catalytic, energy storage, and sensing applications.

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction.

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

Cellulose Nanofiber Biotemplated Palladium Composite Aerogels.

Noble metal aerogels offer a wide range of catalytic applications due to their high surface area and tunable porosity. Control over monolith shape, pore size, and nanofiber diameter is desired in order to optimize electronic conductivity and mechanical integrity for device applications. However, common aerogel synthesis techniques such as solvent mediated aggregation, linker molecules, sol⁻gel, hydrothermal, and carbothermal reduction are limited when using noble metal salts. Here, we present the synthesis of palladium aerogels using carboxymethyl cellulose nanofiber (CNF) biotemplates that provide control over aerogel shape, pore size, and conductivity. Biotemplate hydrogels were formed via covalent cross linking using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) with a diamine linker between carboxymethylated cellulose nanofibers. Biotemplate CNF hydrogels were equilibrated in precursor palladium salt solutions, reduced with sodium borohydride, and rinsed with water followed by ethanol dehydration, and supercritical drying to produce freestanding aerogels. Scanning electron microscopy indicated three-dimensional nanowire structures, and X-ray diffractometry confirmed palladium and palladium hydride phases. Gas adsorption, impedance spectroscopy, and cyclic voltammetry were correlated to determine aerogel surface area. These self-supporting CNF-palladium aerogels demonstrate a simple synthesis scheme to control porosity, electrical conductivity, and mechanical robustness for catalytic, sensing, and energy applications.