Three-dimensional Nanostructured Films Research Articles

One-Step Synthesis of Porous Transparent Conductive Oxides by Hierarchical Self-Assembly of Aluminum-Doped ZnO Nanoparticles.

Transparent conductive oxides (TCOs) are highly desirable for numerous applications ranging from photovoltaics to light-emitting diodes and photoelectrochemical devices. Despite progress, it remains challenging to fabricate porous TCOs (pTCOs) that may provide, for instance, a hierarchical nanostructured morphology for the separation of photoexcited hole/electron couples. Here, we present a facile process for the fabrication of porous architectures of aluminum-doped zinc oxide (AZO), a low-cost and earth-abundant transparent conductive oxide. Three-dimensional nanostructured films of AZO with tunable porosities from 10 to 98% were rapidly self-assembled from flame-made nanoparticle aerosols. Successful Al doping was confirmed by X-ray photoemission spectroscopy, high-resolution transmission electron microscopy, elemental mapping, X-ray diffraction, and Fourier transform infrared spectroscopy. An optimal Al-doping level of 1% was found to induce the highest material conductivity, while a higher amount led to partial segregation and formation of aluminum oxide domains. A controllable semiconducting to conducting behavior with a resistivity change of more than 4 orders of magnitudes from about 3 × 102 to 9.4 × 106 Ω cm was observed by increasing the AZO film porosity from 10 to 98%. While the denser AZO morphologies may find immediate application as transparent electrodes, we demonstrate that the ultraporous semiconducting layers have potential as a light-driven gas sensor, showing a high response of 1.92-1 ppm of ethanol at room temperature. We believe that these tunable porous transparent conductive oxides and their scalable fabrication method may provide a highly performing material for future optoelectronic devices.

Improved plasmon-assisted photoelectric conversion efficiency across entire ultraviolet–visible region based on antenna-on zinc oxide/silver three-dimensional nanostructured films

ZnO has received tremendous attention for applications in photoelectrochemical water splitting, photocatalysis, and photovoltaic devices. However, the photoelectric conversion efficiency of ZnO is limited by the rapid recombination of photoexcited electron–hole pairs and the wide band gap, which allows only a small fraction of the solar spectrum to be absorbed. Recently, substantial research efforts have aimed to increase the photoelectric conversion efficiency across the entire ultraviolet–visible (UV–vis) spectrum by coupling semiconductors such as ZnO with noble metal nanoparticles (NPs). In this study, we compare the performance of a pure ZnO film and ZnO/Ag nanostructured films as photoelectrodes.We show that under broad-spectrum UV–vis illumination, the photocurrent generated in the ZnO/Ag three-dimensional (3D) nanostructured films increases 3.75 times relative to the photocurrent generated in the pure ZnO films. We attribute the high photocurrent to the electric-field enhancement associated with the localized surface plasmon resonance of the Ag NPs, which are present at a high density in the 3D nanostructured films, and to the creation of photoexcited hot electrons in Ag that are transferred to ZnO, promoting electron–hole pair separation. We propose a mechanism to explain the observed enhancement of the photoelectric conversion efficiency.

Triarylphosphine-Stabilized Platinum Nanoparticles in Three-Dimensional Nanostructured Films as Active Electrocatalysts

Ligand-stabilized platinum nanoparticles (Pt NPs) can be used to build well-defined three-dimensional (3-D) nanostructured electrodes for better control of the catalyst architecture in proton exchange membrane fuel cells (PEMFCs). Platinum NPs of 1.7 +/- 0.5 nm diameter stabilized by the water-soluble phosphine ligand, tris(4-phosphonatophenyl)phosphine (TPPTP, P(4-C6H4PO3H2)3), were prepared by ethylene glycol reduction of chloroplatinic acid and subsequent treatment of the isolated nanoparticles with TPPTP. The isolated TPPTP-stabilized Pt NPs were characterized by multinuclear magnetic resonance spectroscopy (31P and 195Pt NMR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). The negatively charged TPPTP-Pt NPs were electrostatically deposited onto a glassy carbon electrode (GCE) modified with protonated 4-aminophenyl functional groups (APh). Multilayers were assembled via electrostatic layer-by-layer deposition with cationic poly(allylamine HCl) (PAH). These multilayer films are active for the key hydrogen fuel cell reactions, hydrogen oxidation (anode) and oxygen reduction (cathode). Using a rotating disk electrode configuration, fully mass-transport limited kinetics for hydrogen oxidation was obtained after 3 layers of TPPTP-Pt NPs with a total Pt loading of 4.2 microg/cm2. Complete reduction of oxygen by four electrons was achieved with 4 layers of TPPTP-Pt NPs and a total Pt loading of 5.6 microg/cm2. A maximum current density for oxygen reduction was reached with these films after 5 layers resulting in a mass-specific activity, i(m), of 0.11 A/mg(Pt) at 0.9 V. These films feature a high electrocatalytic activity and can be used to create systematic changes in the catalyst chemistry and architecture to provide insight for building better electrocatalysts.