We report the rational synthesis of nitrogen-doped zinc oxide (ZnO:N) nanowire arrays, and their implementation as photoanodes in photoelectrochemical (PEC) cells for hydrogen generation from water splitting. Dense and vertically aligned ZnO nanowires were first prepared from a hydrothermal method, followed by annealing in ammonia to incorporate N as a dopant. Nanowires with a controlled N concentration (atomic ratio of N to Zn) up to approximately 4% were prepared by varying the annealing time. X-ray photoelectron spectroscopy studies confirm N substitution at O sites in ZnO nanowires up to approximately 4%. Incident-photon-to-current-efficiency measurements carried out on PEC cell with ZnO:N nanowire arrays as photoanodes demonstrate a significant increase of photoresponse in the visible region compared to undoped ZnO nanowires prepared at similar conditions. Mott-Schottky measurements on a representative 3.7% ZnO:N sample give a flat-band potential of -0.58 V, a carrier density of approximately 4.6 x 10(18) cm(-3), and a space-charge layer of approximately 22 nm. Upon illumination at a power density of 100 mW/cm(2) (AM 1.5), water splitting is observed in both ZnO and ZnO:N nanowires. In comparison to ZnO nanowires without N-doping, ZnO:N nanowires show an order of magnitude increase in photocurrent density with photo-to-hydrogen conversion efficiency of 0.15% at an applied potential of +0.5 V (versus Ag/AgCl). These results suggest substantial potential of metal oxide nanowire arrays with controlled doping in PEC water splitting applications.

A unique gold nanoparticle aggregate (GNA) system has been shown to be an excellent substrate for surface-enhanced Raman scattering (SERS) applications. Rhodamine 6G (R6G), a common molecule used for testing SERS activity on silver, but generally difficult to detect on gold substrates, has been found to readily bind to the GNA and exhibit strong SERS activity due to the unique surface chemistry afforded by sulfur species on the surface. This GNA system has yielded a large SERS enhancement of 107−109 in bulk solution for R6G, on par with or greater than any previously reported gold SERS substrate. SERS activity has also been successfully demonstrated for several biological molecules including adenine, l-cysteine, l-lysine, and l-histidine for the first time on a gold SERS substrate, showing the potential of this GNA as a convenient and powerful SERS substrate for biomolecular detection. In addition, the SERS spectrum of R6G on single aggregates has been measured. We have shown that the special surface properties of the GNA, in conjunction with strong near-IR absorption, make it useful for SERS analysis of a wide variety of molecules.

Photoelectrochemical cells based on traditional and nanostructured ZnO thin films are investigated for hydrogen generation from water splitting. The ZnO thin films are fabricated using three different deposition geometries: normal pulsed laser deposition, pulsed laser oblique‐angle deposition, and electron‐beam glancing‐angle deposition. The nanostructured films are characterized by scanning electron microscopy, X‐ray diffraction, UV‐vis spectroscopy and photoelectrochemical techniques. Normal pulsed laser deposition produces dense thin films with ca. 200 nm grain sizes, while oblique‐angle deposition produces nanoplatelets with a fishscale morphology and individual features measuring ca. 900 by 450 nm on average. In contrast, glancing‐angle deposition generates a highly porous, interconnected network of spherical nanoparticles of 15–40 nm diameter. Mott‐Schottky plots show the flat band potential of pulsed laser deposition, oblique‐angle deposition, and glancing‐angle deposition samples to be −0.29, −0.28 and +0.20 V, respectively. Generation of photocurrent is observed at anodic potentials and no limiting photocurrents were observed with applied potentials up to 1.3 V for all photoelectrochemical cells. The effective photon‐to‐hydrogen efficiency is found to be 0.1%, 0.2% and 0.6% for pulsed laser deposition, oblique‐angle deposition and glancing‐angle deposition samples, respectively. The photoelectrochemical properties of the three types of films are understood to be a function of porosity, crystal defect concentration, charge transport properties and space charge layer characteristics.