Thang Duy Dao

Electrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties

Mesoporous gold (Au) films with tunable pores are expected to provide fascinating optical properties stimulated by the mesospaces, but they have not been realized yet because of the difficulty of controlling the Au crystal growth. Here, we report a reliable soft-templating method to fabricate mesoporous Au films using stable micelles of diblock copolymers, with electrochemical deposition advantageous for precise control of Au crystal growth. Strong field enhancement takes place around the center of the uniform mesopores as well as on the walls between the pores, leading to the enhanced light scattering as well as surface-enhanced Raman scattering (SERS), which is understandable, for example, from Babinet principles applied for the reverse system of nanoparticle ensembles.

Surface-Plasmon-Enhanced Photodriven CO2 Reduction Catalyzed by Metal-Organic-Framework-Derived Iron Nanoparticles Encapsulated by Ultrathin Carbon Layers.

Highly efficient utilization of solar light with an excellent reduction capacity is achieved for plasmonic Fe@C nanostructures. By carbon layer coating, the optimized catalyst exhibits enhanced selectivity and stability applied to the solar-driven reduction of CO2 into CO. The surface-plasmon effect of iron particles is proposed to excite CO2 molecules, and thereby facilitates the final reaction activity.

Effective decoration of Pd nanoparticles on the surface of SnO2 nanowires for enhancement of CO gas-sensing performance

Decoration of noble metal nanoparticles (NPs) on the surface of semiconducting metal oxide nanowires (NWs) to enhance material characteristics, functionalization, and sensing abilities has attracted increasing interests from researchers worldwide. In this study, we introduce an effective method for the decoration of Pd NPs on the surface of SnO2 NWs to enhance CO gas-sensing performance. Single-crystal SnO2 NWs were fabricated by chemical vapor deposition, whereas Pd NPs were decorated on the surface of SnO2 NWs by in situ reduction of the Pd complex at room temperature without using any linker or reduction agent excepting the copolymer P123. The materials were characterized by advanced techniques, such as high-resolution transmission electron microscopy, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The Pd NPs were effectively decorated on the surface of SnO2 NWs. As an example, the CO sensing characteristics of SnO2 NWs decorated with Pd NPs were investigated at different temperatures. Results revealed that the gas sensor exhibited excellent sensing performance to CO at low concentration (1-25ppm) with ultrafast response-recovery time (in seconds), high responsivity, good stability, and reproducibility.

Moiré Nanosphere Lithography

We have developed moiré nanosphere lithography (M-NSL), which incorporates in-plane rotation between neighboring monolayers, to extend the patterning capability of conventional nanosphere lithography (NSL). NSL, which uses self-assembled layers of monodisperse micro/nanospheres as masks, is a low-cost, scalable nanofabrication technique and has been widely employed to fabricate various nanoparticle arrays. Combination with dry etching and/or angled deposition has greatly enriched the family of nanoparticles NSL can yield. In this work, we introduce a variant of this technique, which uses sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal instead of conventional spontaneous self-assembly. Sequential stacking leads to the formation of moiré patterns other than the usually observed thermodynamically stable configurations. Subsequent O2 plasma etching results in a variety of complex nanostructures. Using the etched moiré patterns as masks, we have fabricated complementary gold nanostructures and studied their optical properties. We believe this facile technique provides a strategy to fabricate complex nanostructures or metasurfaces.

Insulator-to-Proton-Conductor Transition in a Dense Metal–Organic Framework

Metal-organic frameworks (MOFs) are prone to exhibit phase transitions under stimuli such as changes in pressure, temperature, or gas sorption because of their flexible and responsive structures. Here we report that a dense MOF, ((CH3)2NH2)2[Li2Zr(C2O4)4], exhibits an abrupt increase in proton conductivity from <10(-9) to 3.9 × 10(-5) S/cm at 17 °C (activation energy, 0.64 eV) upon exposure to humidity. The conductivities were determined using single crystals, and the structures were analyzed by X-ray diffraction and X-ray pair distribution function analysis. The initial anhydrous structure transforms to another dense structure via topotactic hydration (H2O/Zr = 0.5), wherein one-fourth of the Li ions are irreversibly rearranged and coordinated by water molecules. This structure further transforms into a third crystalline structure by water uptake (H2O/Zr = 4.0). The abrupt increase in conductivity is reversible and is associated with the latter reversible structure transformation. The H2O molecules coordinated to Li ions, which are formed in the first step of the transformation, are considered to be the proton source, and the absorbed water molecules, which are formed in the second step, are considered to be proton carriers.

Conversion of Carbon Dioxide by Methane Reforming under Visible‐Light Irradiation: Surface‐Plasmon‐Mediated Nonpolar Molecule Activation

A novel CO2 photoreduction method, CO2 conversion through methane reforming into syngas (DRM) was adopted as an efficient approach to not only reduce the environmental concentration of the greenhouse gas CO2 but also realize the net energy storage from solar energy to chemical energy. For the first time it is reported that gold, which was generally regarded to be inactive in improving the performance of a catalyst in DRM under thermal conditions, enhanced the catalytic performance of Rh/SBA-15 in DRM under visible-light irradiation (1.7 times, CO2 conversion increased from 2100 to 3600 μmol g(-1) s(-1)). UV/Vis spectra and electromagnetic field simulation results revealed that the highly energetic electrons excited by local surface plasmon resonances of Au facilitated the polarization and activation of CO2 and CH4 with thermal assistance. This work provides a new route for CO2 photoreduction and offers a distinctive method to photocatalytically activate nonpolar molecules.

Chemically synthesized nanowire TiO2/ZnO core-shell p-n junction array for high sensitivity ultraviolet photodetector

A sol-gel-based ultrathin TiO2 lamination coating was adapted to a hydrothermally grown ZnO nanowire array to realize an all-oxide ultra-sensitive p-n photodiode. The core-shell heterojunction—the key component of the device—is composed of a 5–10 nm thick p-type Cr-doped TiO2 nanoshell and n-type single-crystalline ZnO nanowires (50 nm radius). Owing to the enhanced light scattering and carrier separation in the core-shell architecture, this device exhibits the highest performance among the ZnO nanowire-based photodetectors. At a moderate reverse bias of −5 V and under ultraviolet light illumination at 104 μW, it shows a switch current ratio of 140 and a responsivity as large as 250 A/W, while it shows nearly no response to the infrared and visible light.

Solar water heating and vaporization with silicon nanoparticles at mie resonances

We propose analytically and demonstrate experimentally that an ensemble of silicon nanoparticles with different sizes can effectively absorb sunlight. Due to the extinction of silicon from UV to near-infrared region, Mie resonances in silicon nanoparticles dramatically enhance the absorption of solar light. In experiment, silicon nanoparticles dispersed in water worked as excellent sunlight-heat transducers that efficiently harvest sunlight to accelerate heating and vaporization of water by nanoscale local heating. Our study opens up the potential of silicon nanoparticles in various solar-thermal applications.

Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules.

From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3′-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes.

Color-Tunable Resonant Photoluminescence and Cavity-Mediated Multistep Energy Transfer Cascade

Color-tunable resonant photoluminescence (PL) was attained from polystyrene microspheres doped with a single polymorphic fluorescent dye, boron-dipyrrin (BODIPY) 1. The color of the resonant PL depends on the assembling morphology of 1 in the microspheres, which can be selectively controlled from green to red by the initial concentration of 1 in the preparation process of the microspheres. Studies on intersphere PL propagation with multicoupled microspheres, prepared by micromanipulation technique, revealed that multistep photon transfer takes place through the microspheres, accompanying energy transfer cascade with stepwise PL color change. The intersphere energy transfer cascade is direction selective, where energy donor-to-acceptor down conversion direction is only allowed. Such cavity-mediated long-distance and multistep energy transfer will be advantageous for polymer photonics device application.