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Surface Engineered CuO Nanowires with ZnO Islands for CO<sub>2</sub> Photoreduction
Wang, Wei-Ning,Wu, Fei,Myung, Yoon,Niedzwiedzki, Dariusz M.,Im, Hyung Soon,Park, Jeunghee,Banerjee, Parag,Biswas, Pratim American Chemical Society 2015 ACS APPLIED MATERIALS & INTERFACES Vol.7 No.10
<P>Large arrays of massively parallel (10<SUP>8</SUP> cm<SUP>–2</SUP>) CuO nanowires were surface engineered with dense ZnO islands using a few pulsed cycles of atomic layer deposition (ALD). These nanowires were subjected to UV–vis radiation-based CO<SUB>2</SUB> photoreduction under saturated humidity (CO<SUB>2</SUB> + H<SUB>2</SUB>O mixture) conditions. We monitored CO<SUB>2</SUB> to CO conversion, indicating the viability of these nanostructures as potential photocatalysts. High-resolution transmission electron microscopy and atomic force microscopy indicated an island growth mechanism of ZnO epitaxially depositing on pristine, single crystal CuO nanowire surface. Photoluminescence and transient absorption spectroscopy showed a very high density of defects on these ZnO islands which trapped electrons and enhanced their lifetimes. Peak CO conversion (1.98 mmol/g-cat/hr) and quantum efficiency (0.0035%) were observed in our setup when the ZnO islands impinged each other at 1.4 nm (8 cycles of ALD) diameter; at which point ZnO island perimeter lengths maximized as well. A mechanism whereby simultaneous H<SUB>2</SUB>O oxidation and CO<SUB>2</SUB> reduction occurred in the active perimeter region between CuO nanowire and ZnO islands is proposed to explain the observed photoconversion of CO<SUB>2</SUB> to CO.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/aamick/2015/aamick.2015.7.issue-10/am508590j/production/images/medium/am-2014-08590j_0007.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/am508590j'>ACS Electronic Supporting Info</A></P>