title: Nitrogen-doped ZnO nanowire arrays for photoelectrochemical water splitting.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, USA.
authors.forename: Xunyu
authors.initials: X
authors.lastname: Yang
authors.forename: Abraham
authors.initials: A
authors.lastname: Wolcott
authors.forename: Gongming
authors.initials: G
authors.lastname: Wang
authors.forename: Alissa
authors.initials: A
authors.lastname: Sobo
authors.forename: Robert Carl
authors.initials: RC
authors.lastname: Fitzmorris
authors.forename: Fang
authors.initials: F
authors.lastname: Qian
authors.forename: Jin Z
authors.initials: JZ
authors.lastname: Zhang
authors.forename: Yat
authors.initials: Y
authors.lastname: Li
mesh_terms: D053770:Nanowires / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010782:Photolysis; D014867:Water / Q000737:chemistry*; D015034:Zinc Oxide / Q000737:chemistry*
chemical_list: D014867:Water; D009584:Nitrogen; D015034:Zinc Oxide