Electrochemical nitrate reduction over bimetallic Pd-Sn nanocatalysts with tunable selectivity toward benign nitrogen.

Nitrate is recognized as a highly impactful water contaminant among various pollutants in water. To address the ever-growing demand for water purification, this work investigates the bimetallic palladium (Pd) and tin (Sn) catalysts, which are electrochemically deposited on stainless steel mesh support (Pd-Sn/SS) for the selective conversion of harmful nitrate (NO3-) into benign nitrogen (N2) gas. Results indicate that the bimetallic composition in Pd-Sn/SS electrodes substantially influenced the reaction route for nitrate reduction as well as the performance of nitrate transformation and nitrogen selectivity. It is found that the electrode prepared from Pd:Sn = 1:1 (mole ratio) demonstrates an outstanding nitrate conversion of 95%, nitrogen selectivity of 88%, and nitrogen yield of 82%, which outperform many reported values in the literature. The electrochemically synthesized bimetallic electrode proposed herein enables a new insight for promoting the reactivity and selectivity of nitrate reduction in water.

Synthesis and characterization of bicontinuous cubic poly(3,4-ethylene dioxythiophene) gyroid (PEDOT GYR) gels.

We describe the synthesis and characterization of bicontinuous cubic poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer gels prepared within lyotropic cubic poly(oxyethylene)10 nonylphenol ether (NP-10) templates with Ia3[combining macron]d (gyroid, GYR) symmetry. The chemical polymerization of EDOT monomer in the hydrophobic channels of the NP-10 GYR phase was initiated by AgNO3, a mild oxidant that is activated when exposed to ultraviolet (UV) radiation. The morphology and physical properties of the resulting PEDOT gels were examined as a function of temperature and frequency using optical and electron microscopy, small-angle X-ray scattering (SAXS), dynamic mechanical spectroscopy, and electrochemical impedance spectroscopy (EIS). Microscopy and SAXS results showed that the PEDOT gels remained ordered and stable after the UV-initiated chemical polymerization, confirming the successful templated-synthesis of PEDOT in bicontinuous GYR nanostructures. In comparison to unpolymerized 3,4-ethylenedioxythiophene (EDOT) gel phases, the PEDOT structures had a higher storage modulus, presumably due to the formation of semi-rigid PEDOT-rich nanochannels. Additionally, the storage modulus (G') for PEDOT gels decreased only modestly with increasing temperature, from ∼1.2 × 10(5) Pa (10 °C) to ∼7 × 10(4) Pa (40 °C), whereas G' for the NP-10 and EDOT gels decreased dramatically, from ∼5.0 × 10(4) Pa (10 °C) to ∼1.5 × 10(2) Pa (40 °C). EIS revealed that the impedance of the PEDOT gels was smaller than the impedance of EDOT gels at both high frequencies (PEDOT ∼10(2) Ω and EDOT 2-3 × 10(4) Ω at 10(5) Hz) and low frequencies (PEDOT 10(3)-10(5) Ω and EDOT ∼5 × 10(5) Ω at 10(-1) Hz). These results indicated that PEDOT gels were highly ordered, mechanically stable and electrically conductive, and thus should be of interest for applications for which such properties are important, including low impedance and compliant coatings for biomedical electrodes.

Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces.

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material.

The preparation of superhydrophobic surfaces of hierarchical silicon nanowire structures.

Superhydrophobic surfaces are prepared by fabricating silicon nanowires to enhance the surface roughness and then modifying the chemical nature of the surface with a self-assembled octadecyltrichlorosilane monolayer to lower the surface energy. All the processes are performed near room temperature. The dynamic contact angle data demonstrate that the water droplet on these surfaces of nanowires can exhibit a transition from the Wenzel state to the Cassie state by simply controlling the etching time. The hierarchical structure is constructed by fabricating the nanopillars (i.e. nanowires) on top of the regular pillar-like silicon wafers. As a consequence, superhydrophobicity could be achieved much more effectively by applying the hierarchical structure.