Lichun Liu

Wet-Chemical Synthesis of Palladium Nanosprings

We report a methodology for synthesis of palladium (Pd) nanospring structures using an anodic aluminum oxide (AAO) membrane template and facile electrochemical deposition. The hydroxyl-terminated surfaces of alumina nanochannels and localized hydrogen evolution contribute to the growth of Pd atoms at peripheral positions of the alumina nanochannels in the presence of an effectual electric potential and a plating solution consisting of PdCl(2), CuCl(2), and HCl. Structural characterization including EDS line analysis and element mapping revealed Pd nanodomains curling up on the Cu nanorods. A clear Pd nanospring shape was observed after selectively removing Cu. The lengths of the nanosprings were dictated by the charges transported through electrodeposition, and the diameters of the nanosprings were tunable by altering the diameter of the alumina nanochannels. Screw dislocation is the most probable crystallographic defect responsible for the formation of coiled Pd nanostructures. Pd nanosprings have potential applications in nanomachines, nanosensors, nanoinductors, and metamaterials. We anticipate that our synthesis method will motivate and inform the synthesis of more advanced nanomaterials.

Galvanically Replaced Hollow Au–Ag Nanospheres: Study of Their Surface Plasmon Resonance

We synthesized hollow Au-Ag nanospheres (NSs) by employing a galvanic replacement reaction between HAuCl4 and Ag NSs. Uniform Ag NSs with controllable sizes were synthesized as sacrificial templates by a seed-mediated strategy. The atomic ratio of Au to Ag in Au-Ag NSs was tunable by controlling the reagent concentration. UV-vis extinction spectra acquired from well-dispersed colloidal NS solutions were used to investigate the optical properties of the solutions. In addition to a common dipole mode exhibited on most transition metal nanoparticles, we observed a quadrupole plasmon resonance mode when the diameters of the Ag and Au-Ag NSs were larger than 100 nm. The quadrupole and dipole peaks both shifted to longer wavelengths with increased Au content in Au-Ag NSs. The experimental observation of optical properties of hollow Au-Ag NSs was compared with the theoretical simulation using DDA calculation, showing a good agreement.

Nanoparticle films as a conducting layer for anodic aluminum oxide template-assisted nanorod synthesis

A simple, inexpensive, and robust methodology was developed to fabricate conductive film substrates by mechanically packing nanoparticles (NPs) on one side of anodic aluminum oxide (AAO). Gold, silver NPs, and carbon nanotubes were used as building blocks in the synthesis of conductive film substrates, upon which perpendicular nanorod arrays and colloidal free-standing nanorods were easily constructed. Characterizations by field emission scanning electron microscopy (FE-SEM) and optical dark-field microscopy confirmed the validity of the conductive NP film substrates on the AAO template. This contribution could provide a convenient and low-cost means for the fabrication of various conductive substrates on AAO.

Synthesis of bimetallic Pt/Pd nanotubes and their enhanced catalytic activity in methanol electro-oxidation

In this work, we successfully synthesized a vertically-aligned bimetallic Pt/Pd nanotube array by using anodic aluminum oxide (AAO) template-assisted electro-deposition. The resulting nanostructures exhibited higher catalytic activity in methanol oxidation than either individual constituent (Pt or Pd). The facile synthesis of the Pt/Pd tubular nanostructure was inspired by the previously developed thin-walled Pd nanotube formation mechanism, which takes advantage of the surface hydroxyl chemistry of the AAO template. The content of Pt in the bimetallic Pt/Pd nanotubes could reach up to 50%. The inner and outer walls of the perpendicular open Pt/Pd nanotubes increased the ratio of the surface area to the mass relative to the solid nanorod structure, resulting in a higher current density in methanol oxidation. More importantly, the synergistic electronic effect between Pt and Pd gave rise to the enhanced catalytic activity in methanol oxidation, as evidenced from comparisons of the onset potentials and CO oxidation behaviors. Thus, vertically-aligned bimetallic Pt/Pd nanotubes may act as a better catalyst in methanol oxidation than the single-component Pt counterpart.

A series of organic–inorganic hybrid materials consisting of flexible organic amine modified polyoxomolybdates: synthesis, structures and properties

A series of organic–inorganic hybrid complexes based on different types of polyoxomolybdates and transition metal complexes, namely, [Zn2(TPMA)2(H2P2Mo5O23)]·11H2O (1), [Zn2(TPMA)2(Mo8O26)] (2), [Co2(TPMA)2(Mo8O26)] (3), [Ni2(TPMA)2(Mo8O26)(H2O)2] (4), [Ni2(TPMA)2(2-PA)(H2O)](PMo12O40) (5) [Cu2(TPMA)2(Mo8O26)] (6), 2[Cu(TPMA)(CrMo6(OH)6O18)]·H[Cu2(TPMA)2(CrMo6(OH)6O18)]·4H2O (7) (TPMA = Tris[(2-pyridyl)methyl]amine, 2-PA = 2-picolinic acid), have been successfully synthesized under hydrothermal conditions. All complexes were characterized by single-crystal X-ray structural analysis, powder X-ray diffraction, IR spectroscopy and TG analysis. All the complexes showed polyoxomolybdate-based zero-dimensional (0D) structures, and could be further extended into three-dimensional (3D) supramolecular frameworks through hydrogen bonding interactions. In addition, the electrochemical properties of complexes 1–7 have been investigated. Interestingly, some complexes have efficient photocatalytic activities to degradate pararosaniline hydrochloride dye molecules.

Superhydrophobic hBN-Regulated Sponges with Excellent Absorbency Fabricated Using a Green and Facile Method

The world faces severe environmental, human and ecological problems when major oil spills and organic discharges are released into the environment. And so it is imperative to develop tools and high performance innovative materials that can efficiently absorb these organic discharges. Furthermore, green, facile methods to produce these advanced materials are also needed. In this paper, we demonstrate a novel porous supersponge based on melamine coated with hBN. This superhydrophobic sponge (with a contact angle >150°) exhibits excellent absorption performance for oils and organic solvents, including good selectivity, high capacity (up to 175 g·g−1) and extraordinary recyclability (less than 20% decline after 30 cycles of absorption/squeezing). The synthetic procedure required only ultrasonication and immersion of the sponge in aqueous hBN solution, being a green, cost-effective and scalable production methodology. By virtue of the straightforward and cost-effective fabrication method, along with the excellent absorption performance, hBN-decorated sponges have great promise for real world practical application in the field of oil spills and organic leakage cleanup.

Single inorganic-organic hybrid photovoltaic nanorod

We demonstrate that single photovoltaic (PV) nanorods can be readily fabricated by electrochemical processing in solution-phase under ambient conditions. A porous Au nanorod electrode in the core of the PV nanorod was central to both its structural formation and superior performance. We examined an intrinsically conducting polymer (polypyrrole) and an inorganic semiconductor (cadmium selenide) as precursor materials. Through an extremely simple and cost-effective fashioning process (solution-phase, room temperature), unadorned PV nanorods with up to 1.1% power conversion efficiency were obtained.

Electrodeposition of Rhodium Nanowires Arrays and Their Morphology-Dependent Hydrogen Evolution Activity

This work reports on the electrodeposition of rhodium (Rh) nanowires with a controlled surface morphology synthesized using an anodic aluminum oxide (AAO) template. Vertically aligned Rh nanowires with a smooth and coarse morphology were successfully deposited by adjusting the electrode potential and the concentration of precursor ions and by involving a complexing reagent in the electrolyte solution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses were used to follow the morphological evolution of Rh nanowires. As a heterogeneous electrocatalyst for hydrogen evolution reactions (HER), the coarse Rh nanowire array exhibited an enhanced catalytic performance respect to smooth ones due to the larger surface area to mass ratio and the higher density of catalytically active defects, as evidenced by voltammetric measurements and TEM. Results suggest that the morphology of metallic nanomaterials could be readily engineered by electrodeposition. The controlled electrodeposition offers great potential for the development of an effective synthesis tool for heterogeneous catalysts with a superior performance for wide applications.

Functional Magnetic Nanoparticles for Clinical Application: Electrochemical Immunoassay of Hepatitis B Surface Antigen and α-Fetoprotein

This work reports an efficient method to quantify the Hepatitis B surface antigen and α-fetoprotein in human serum using a functional magnetic nanoparticle-assisted sandwich-type electrochemical immunoassay. The Fe 3 O 4 magnetic nanoparticles were first modified with carboxyl functional groups to permit stable bioconjugation to the amine groups of most biological targets. The primary antibodies were then covalently stained on the surface of the functional magnetic nanoparticles, followed by the analyte and secondary antibodies, resulting in a sandwich-type (antibody-antigen-antibody/enzyme) immune complex. The secondary antibodies were labeled with horseradish peroxidase for the catalytic oxidation of 2-aminophenol to yield electrochemically reducible molecules. The separation using an external magnetic field guaranteed fast and reliable purification and enrichment of analytes. Quantitative analysis was performed upon representative clinical targets: Hepatitis B surface antigen and α-fetoprotein in human serum. The detection limits were 0.06 ng/mL for the former and 0.5 ng/mL for the latter, which were about 10 times lower than values obtained by conventional enzyme-linked immunosorbent assays. The reported method may be adopted as a general strategy for the sensitive and selective determination of additional proteins and biological molecules.

Platinum-Coated Porous Gold Nanorods in Methanol Electrooxidation: Dependence of Catalytic Activity on Ligament Size

Here we demonstrate that, in the dealloying process of Au-Ag nanorods, temperature is the key parameter for producing porous Au nanorods with tunable ligament sizes. The vertically aligned Au-Ag alloy nanorods were first synthesized by the electrochemical co-deposition of Au and Ag onto anodic aluminum oxide (AAO) membrane templates. Porous Au nanorods were then obtained by selectively etching Ag away from the precursor Au-Ag alloy nanorods. Control of the ligament size was achieved by controlling the dealloying temperature. Pt deposited on the porous Au nanorods with smaller ligaments exhibited a higher catalytic activity during methanol electrooxidation than those deposited on nanorods with larger ligaments produced by dealloying at higher temperatures. The strong dependence of the catalytic activity on the ligament size of porous Au is principally due to different amounts of carbon monoxide (CO) generated during methanol electrooxidation. Less CO was generated as the ligament size decreased. This finding is of importance for developing highly efficient cathode materials for carrying out methanol electrooxidation in practical applications in which porous Au with a large surface area is used as a supporting substrate.