Freestanding monolayered nanoporous gold films with high electrocatalytic activity via interfacial self-assembly and overgrowth
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Nanoporous gold freestanding films (NPG FSFs) have been fabricated via overgrowth of gold onto self-assembled monolayers of gold nanocrystals at planar fluid–fluid interfaces. The resulting NPG FSFs are ligand-free on their surfaces and their sizes can be as large as several cm2. The NPG FSFs are fairly mechanically robust; their effective Young's moduli are of the order of about 10 GPa. The NPG FSFs exhibit efficient electrocatalytic activity for methanol oxidation with an excellent electrochemical endurance, which is attributed to the presence of high-index facets on the curved surfaces of gold ligaments in the NPG FSFs. It is found that the catalytic performance of as-prepared NPG FSFs is related to the curved-to-flat surface area ratios of gold ligaments in NPG FSFs. The highly curved surface areas in the NPG FSFs can be increased via optimizing the concentration of HAuCl4 and the citrate to HAuCl4 molar ratio in the electroless plating solution.Keywords:
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For the application of high-surface-area nanoporous platinum (Pt) to catalytic device, electrodes and sensors, dealloying technique, which can synthesize nanoporous Pt, was combined with surface alloying technique. As a result, nanoporous structure with ligament and pore sizes below 10 nm was successfully fabricated on the Pt plate surface. Cyclic voltammetry in H2SO4 indicated that the nanoporous structure increases the true surface area by 170 times. The approximation by spherical pore model suggested that the nanoporous surface layer has a thickness of 200 nm.
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This work reports the effects of metallic glass precursors on the catalytic performance of nanoporous metals. Pd-based multicomponent nanoporous metals with similar nanoporous structure were successfully fabricated by electrochemically dealloying the Pd20Ni60P17B3 and Pd20Ni20Cu40P17B3 metallic glass precursors at the critical dealloying potentials. It was found that the glassy precursors with different chemical compositions result in different doping elements in the as-obtained nanoporous metals and thus lead to different catalytic activities.
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3D nanoporous graphene shows excellent physics and electrochemical performance in the fields of energy storage and conversion due to its high-quality and unique interconnected structure. Nanoporous metals, especially nanoporous Ni and nanoporous Cu, have high catalysis for the synthesis of high-quality 3D nanoporous graphene. This chapter presents an overview of the most recent research about the 3D nanoporous graphene, heteroatoms-doped nanoporous graphene, and the nanoporous graphene-based composite materials synthesized by using nanoporous Ni and nanoporous Cu.
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The electrostatic binding and metal coordination between metal ions and Langmuir monolayers or LB films are discussed, and their effects on the monolayer 2D structure and related phase behavior are analyzed. The interfacial recognition and sensing for metal ions by Langmuir monolayers are also shown. Langmuir monolayers and LB films as 2D template to induce the 2D-oriented crystal growth via metal/monolayer binding is especially demonstrated. The abnormal catalytic characteristics, the functions and devices of metal-incorporated Langmuir monolayers and LB films are displayed by some examples. The review also shows the application of metal-chelating lipid monolayers on the interfacial study of bio-macromolecules. The review suggests the great roles of metal/monolayer binding in alternating monolayer structures and the assembly of functional metal complexes.
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The molecular interactions of monolayers composed of cyclic and linear forms of surfactins (SFs) were evaluated through atomic force microscopy (AFM) together with a Langmuir monolayer technique. The surface pressure (π)-area per molecule (A) isotherm of a pure cyclic surfactin (CSF) monolayer exhibited a liquid expanded (Le) monolayer, while that of a pure linear surfactin (LSF) monolayer exhibited a liquid condensed (Lc) monolayer, demonstrating that the CSFs are in a rather loose molecular packing state owing to its bulky heptapeptide ring. The plots of the mean area per molecule of the CSF/LSF monolayers were well fitted to the ideal curves, suggesting that ideal mixing occurs, or that the two components are immiscible in a monolayer. The AFM images of the CSF/LSF monolayers transferred at 25 mN/m gave phase-separated microdomain structures, indicating that the CSFs and LSFs are almost immiscible and separated into a CSF-rich and LSF-rich phases, as suggested from the analysis of the mean area per molecule of the monolayers. Our results clearly demonstrated that the cleavage of the cyclic heptapeptide headgroup of CSF drastically changes its molecular packing state in a monolayer and that AFM observation combined with the Langmuir monolayer technique is quite useful to explore the manner of self-assembly of a binary system of microbial products such as CSFs and LSFs.
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